Amphoteric Ethyl Methacrylate Copolymers and Use Thereof

ABSTRACT

The present invention relates to amphoteric copolymers which comprise ethyl methacrylate, if appropriate a N-vinyllactam compound, at least one monoethylenically unsaturated carboxylic acid and at least one compound with α,β-ethylenically unsaturated double bond and at least one cationogenic and/or cationic group in copolymerized form, to cosmetic and pharmaceutical compositions which comprise such copolymers, to preparation methods, and to the use of these copolymers.

The present invention relates to amphoteric copolymers which compriseethyl methacrylate, if appropriate a N-vinyllactam compound, at leastone monoethylenically unsaturated carboxylic acid and at least onecompound with α,β-ethylenically unsaturated double bond and at least onecationogenic and/or cationic group in copolymerized form, to cosmeticand pharmaceutical compositions which comprise such copolymers, toproduction methods, and to the use of these copolymers.

PRIOR ART

Polymers with film-forming properties have found diverse uses in thepharmaceutical and cosmetics sector.

In pharmacy, they serve, for example, as coatings or binders for soliddrug forms.

In cosmetics, polymers with film-forming properties are used inter aliafor setting the hair, improving the structure of the hair and shapingthe hair. They serve, for example, as conditioners for improving the dryand wet combability, the feel to the touch, the shine and theappearance, and impart antistatic properties to the hair. Requirementswhich are placed on film-forming polymers for use as setting resins are,for example, strong hold (even at high atmospheric humidity), highflexural rigidity and elasticity, ability to be washed out of the hair,compatibility in the formulation and a pleasant feel of the hair treatedtherewith. The provision of products with a complex profile ofproperties often presents difficulties. There is thus a need forfilm-forming polymers for hair cosmetic compositions which are able toform essentially smooth, tack-free films, in particular have a goodsetting action and at the same time impart to the hair good sensoryproperties, such as elasticity, a pleasant feel and volume.

In hairspray formulations, good propellant gas compatibility,suitability for use in low-VOC formulations (VOC=volatile organiccompounds), good sprayability, good solubility in water oraqueous/alcoholic solvent mixtures and good ability to be washed out arealso desired.

Copolymers based on (meth)acrylate which are water-soluble in alkalineconditions are often used in the field of cosmetics as hair-settingcompositions.

EP-A 491 629 describes an aerosol preparation comprising a neutralizedtetrapolymer consisting of a) 4 to 6% by weight of acrylic acid, b) 42to 52% by weight of N-vinylpyrrolidone, c) 15 to 25% by weight ofN-tert-butylacrylamide and d) 20 to 26% by weight of ethyl methacrylate.

DE 2 817 369 describes copolymers in which at least three of the monomerunits have a methacrylic acid structure, where the copolymers consist of22 to 64 mol % of N,N-dimethylaminoethyl methacrylate, 13 to 72 mol % ofmethyl methacrylate, 6 to 23 mol % of methacrylic acid and 0 to 22 mol %of at least one N-substituted alkyl(meth)acrylamide.

EP-A 62 002 describes terpolymers which are prepared by copolymerizationof a) 40 to 60% by weight of a N-alkylacrylamide orN-alkylmethacrylamide having 1 to 4 carbon atoms in the alkyl moietywith b) 35 to 50% by weight of a C₁-C₄-hydroxyalkyl ester or preferablyC₁-C₄-alkyl ester of acrylic acid or methacrylic acid and c) 3 to 11% byweight of an α,β-unsaturated monocarboxylic acid or dicarboxylic acid.

EP-A 100 890 describes copolymers obtained by free-radicalcopolymerization of from 20 to 75 parts by weight of at least oneC₂-C₂₀-alkyl ester of (meth)acrylic acid, 5 to 50 parts by weight of atleast one nitrogen-containing, neutrally reacting water-soluble monomer,1 to 25 parts by weight of at least one cationic group-containingmonomer and 1 to 25 parts by weight of at least one olefinicallyunsaturated C₃-C₅-carboxylic acid copolymerizable with a), b) and c),which have a K value in accordance with Fikentscher of from 15 to 75measured in ethanol at 25° C.

DE 42 23 006 describes hair-treatment compositions which comprise, asfilm former, copolymers which are obtainable by copolymerization of (a)30 to 80% by weight of an acrylic or methacrylic ester which in eachcase as homopolymer has a glass transition temperature of more than 20°C. or of mixtures of acrylic and methacrylic esters which producecopolymers with a glass transition temperature of more than 20° C.during the copolymerization, (b) 5 to 25% by weight of acrylic acid,methacrylic acid or mixtures thereof and (c) 10 to 45% by weight ofN-vinylpyrrolidone, N-vinylcaprolactam or mixtures thereof in thepresence of free-radical-forming polymerization initiators, and which,in the form of the free carboxylic acid groups, have K values(determined in accordance with H. Fikentscher in 1% strength by weightsolution in ethanol at 25° C.) of from 10 to 80, wherein the copolymersare prepared by the process of precipitation polymerization.

EP-A 805 169 describes copolymers obtainable by free-radicalpolymerization of a mixture of

-   a) 30 to 72% by weight of t-butyl acrylate or t-butyl methacrylate    or a mixture thereof,-   b) 10 to 28% by weight of acrylic acid or methacrylic acid or a    mixture thereof and-   c) 0 to 60% by weight of at least one further free-radically    copolymerizable monomer.

EP-A 256 458 describes copolymers for use as hair fixatives obtained byfree-radical polymerization of

-   a) 20 to 60% by weight of vinylpyrrolidone,-   b) 20 to 60% by weight of an acrylamide mono- or dialkylated on the    N atom and having 1 to 8 carbon atoms in the alkyl radical or their    mixtures,-   c) 5 to 60% by weight of an alkyl or hydroxyalkyl ester of acrylic    or methacrylic acid having 1 to 4 carbon atoms in the alkyl radical    or 2 to 4 carbon atoms in the hydroxyalkyl radical or mixtures of    these esters or 3 to 12% by weight of acrylic acid or methacrylic    acid or 2 to 48% by weight of an alkyl or hydroxyalkyl ester of    acrylic acid or methacrylic acid having 1 to 4 carbon atoms in the    alkyl or 2 to 4 carbon atoms in the hydroxyalkyl radical or mixtures    of these esters and 3 to 12% by weight of acrylic acid or    methacrylic acid, where the % by weight are based on the total    weight of the monomers, which is soluble in lower alcohols having 1    to 4 carbon atoms and has a K value of from 15 to 75.

U.S. Pat. No. 3,405,084 describes terpolymers comprising 20 to 70% byweight of acrylate, 25 to 75% by weight of N-vinylpyrrolidone and 3 to25% by weight of an acrylic acid.

EP-A 491 629 describes hair cosmetic preparations which comprise, asfilm former, a tetrapolymer of 4 to 6% by weight of acrylic acid, 20 to26% by weight of ethyl methacrylate, 42 to 52% by weight ofN-vinylpyrrolidone and 15 to 25% by weight of N-tert-butylacrylamide.

U.S. Pat. No. 3,577,517 describes hair lacquers and aerosol preparationswhich comprise neutralized solution polymers of 5 to 40% by weight of a(meth)acrylic ester with aliphatic C₈-C₁₈-alcohols, 6 to 35% by weightof (meth)acrylic acid and 25 to 89% by weight of a further vinylmonomer, a water-soluble organic solvent, and propellant.

U.S. Pat. No. 3,927,199 describes interpolymers of 30 to 60% by weightof N-alkyl(meth)acrylamide, 12 to 18% by weight of an ethylenicallyunsaturated acid, 20 to 55% by weight of further monomers.

EP-A 257 444 describes terpolymers obtained by free-radicalpolymerization of from 20 to 50% by weight of vinylpyrrolidone, 40 to70% by weight of tert-butyl acrylate or tert-butyl methacrylate and 2 to15% by weight of acrylic acid or methacrylic acid whose carboxyl groupsare, if appropriate, 5 to 100%, preferably 50 to 90%, neutralized by anorganic amine and which have a K value of from 10 to 60.

U.S. Pat. No. 5,045,617 describes zwitterionic terpolymers consisting ofa vinyllactam, an aminoalkylacrylamide or aminoalkyl acrylate and apolymerizable carboxylic acid.

OBJECT OF THE INVENTION

Stricter environmental regulations and growing ecological awarenessincreasingly demand ever lower fractions of volatile organic components(VOC) in, for example, hairsprays.

According to the VOC guidelines (solvent guideline), VOCs are volatileorganic compounds which, at 293.15 K, have a vapor pressure of 0.01 kPaor more and, under the particular use conditions, have a correspondingvolatility.

The VOC content in hairsprays is essentially set by the nonaqueoussolvents and the propellants. For this reason, instead of nonaqueoussolvents, recourse is increasingly being made to water as solvent. Thisreplacement of the organic solvents, however, is associated withproblems, particularly in the field of hairspray formulations.

Thus, formulations of the abovementioned film-forming polymers from theprior art which satisfy the corresponding VOC regulations, are, forexample, not sprayable or are sprayable only after further dilution andare thus only of limited suitability for use in hairsprays. This in turnleads to films which sometimes do not have the required mechanicalquality and thus inadequate setting action and poor hold for the hair.

Requirements placed on hair-setting resins, are, for example, stronghold at high atmospheric humidity, elasticity, good ability to be washedout of the hair, compatibility in the formulation, greatest possiblesmoothness and low tack of the film formed and a pleasant feel of thehair treated therewith. In the case of spray formulations, a homogeneousdistribution of small droplets for forming a fine spray pattern is alsodesired in particular. The provision of products with a complex profileof properties often presents difficulties.

An object of the invention was to provide polymers suitable for cosmeticlow-VOC preparations which, upon use, lead to strong hold at highatmospheric humidity, good ability to be washed out of the hair,compatibility in the low-VOC formulation, good rheological properties,such as high flexural rigidity and elasticity, and greatest possiblesmoothness and low tack of the film formed and a pleasant feel of thehair treated therewith, and in the case of the use in a low-VOC spraypreparation produce a good spray pattern.

This object is achieved through the provision of copolymers obtainableby free-radical polymerization of a monomer mixture M comprising

-   a) 30 to 80% by weight of ethyl methacrylate or-    30 to 80% by weight of a mixture of ethyl methacrylate and at least    one compound of the general formula I different from ethyl    methacrylate    -   in which    -   R¹ is H or CH₃,    -   R² is C₁-C₄-alkyl,-   b) 0 to 40% by weight of at least one N-vinyllactam compound,-   c) 5 to 35% by weight of at least one monoethylenically unsaturated    carboxylic acid,-   d) 0.1 to 30% by weight of at least one compound with a    free-radically polymerizable, α,β-ethylenically unsaturated double    bond and at least one cationogenic and/or cationic group per    molecule,-   e) 0 to 20% by weight if appropriate of further free-radically    polymerizable monomers different from a), b), c) and d),-    where the fractions of components a) to e) add up to 100% by weight    and where the monomer mixture M comprises at least 20% by weight of    ethyl methacrylate.

In a preferred embodiment of the invention, the ratio of the total molaramount of the carboxyl and carboxylate groups to the total molar amountof the cationogenic and cationic groups is at least 2, particularlypreferably at least 3, in particular at least 4 and very particularlypreferably at least 5.

Total molar amount of the carboxyl and carboxylate groups is understoodas meaning the sum of all protonated and deprotonated carboxyl groups,i.e. all COOH and COO⁻ groups.

The total molar amount of the cationogenic and cationic groups isunderstood as meaning the sum of all cationic groups and cationogenicgroups, i.e. groups which can be converted into cationic groups.

In the text below, compounds which can be derived from acrylic acid andmethacrylic acid are sometimes referred to in short by adding thesyllable “(meth)” to the compound derived from acrylic acid.

For the purposes of the present invention, water-soluble monomers andpolymers are understood as meaning monomers and polymers which dissolvein water in an amount of at least 1 g/l at 20° C. Water-dispersiblemonomers and polymers are understood as meaning monomers and polymerswhich disintegrate into dispersible particles under the application ofshear forces, for example by stirring. Hydrophilic monomers arepreferably water-soluble or at least water-dispersible. The copolymersaccording to the invention are generally water-soluble.

The copolymers according to the invention are suitable in a particularlyadvantageous manner for use in cosmetic compositions, in particular inhair-treatment compositions. They serve preferably for producing elastichairstyles coupled with strong hold. Advantageously, they areadditionally characterized both by good propellant gas compatibility,and also good solubility in water or aqueous/alcoholic solvent mixtures.They can thus be formulated either to give hairsprays with high contentsof propellant gas (VOC at least 85% by weight) or to give formulationswith low VOC values (generally not more than 55% by weight, based on thetotal weight of the composition). In any case, the hairsprayformulations are characterized by very good sprayability and ability tobe washed out of the hair.

Component a)

Component a) is ethyl methacrylate or a mixture of ethyl methacrylateand at least one further compound different from ethyl methacrylatechosen from the group consisting of methyl (meth)acrylate, ethylacrylate, methyl ethacrylate, n-propyl (meth)acrylate, isopropyl(meth)acrylate, n-propyl ethacrylate, ethyl ethacrylate, isopropylethacrylate, n-butyl (meth)acrylate, n-butyl ethacrylate, tert-butyl(meth)acrylate, tert-butyl ethacrylate, isobutyl (meth)acrylate,isobutyl ethacrylate, sec-butyl (meth)acrylate, butyl ethacrylate.

The copolymers according to the invention comprise, based on the totalweight of the monomers used for the polymerization at least 30% byweight, preferably at least 40% by weight, particularly preferably atleast 50% by weight and at most 80% by weight, preferably at most 75% byweight and in particular at most 70% by weight, of component a) incopolymerized form.

As component a), preference is given to ethyl methacrylate or a mixturecomprising or consisting of ethyl methacrylate and tert-butyl acrylate.

If ethyl methacrylate is present in a mixture with further(meth)acrylates as component a), then the fraction of ethyl methacrylatein the monomer mixture M of all monomers to be polymerized is at least20% by weight.

Component b)

N-Vinyllactams suitable as monomers b) are unsubstituted N-vinyllactamsand N-vinyllactam derivatives, which can have, for example, one or moreC₁-C₆-alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, tert-butyl etc. These include, for example,N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam,N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone,N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone,N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam andmixtures thereof.

The monomer mixture M to be polymerized comprises 0 to 40% by weight ofcomponent b).

In a preferred embodiment of the invention, the monomer mixture M to bepolymerized comprises no component b).

In a further preferred embodiment, the monomer mixture M to bepolymerized comprises at least 3, preferably at least 5, particularlypreferably at least 10 and at most 35, preferably at most 30 andparticularly preferably at most 25% by weight, of component b).

Component c)

Based on the total weight of the monomers used for the polymerization,the copolymers according to the invention comprise at least 5% byweight, preferably at least 10% by weight, particularly preferably atleast 20% by weight and at most 35% by weight, preferably at most 30% byweight, particularly preferably at most 27% by weight and especially atmost 25% by weight, of at least one monoethylenically unsaturatedcarboxylic acid as component c) in copolymerized form.

For the preparation of the copolymers, the monoethylenically unsaturatedcarboxylic acid c) can be used in partially or completely deprotonatedform. The counterions thereof then preferably derive from bases asdescribed below for adjusting the pH during the polymerization or of theresulting polymers.

The monoethylenically unsaturated carboxylic acid c) is chosen from thegroup consisting of acrylic acid, methacrylic acid, ethacrylic acid,alpha-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride,itaconic acid, citraconic acid, mesaconic acid, glutaconic acid,aconitic acid and fumaric acid. The components c) further include thehalf-esters of monoethylenically unsaturated dicarboxylic acids having 4to 10, preferably 4 to 6, carbon atoms, e.g. of maleic acid, such asmonomethyl maleate. c) also includes the salts of the abovementionedacids, in particular the sodium, potassium and ammonium salts. Thecomponents c) can be used as they are or as a mixture with one another.The weight fractions given all refer to the acid form.

Component c) is preferably chosen from the group consisting of acrylicacid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid,crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconicacid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acidand mixtures thereof, particularly preferably acrylic acid, methacrylicacid and their binary mixtures and especially methacrylic acid.

The invention preferably provides a copolymer according to the inventionwhere component c) of the monomer mixture M consists of methacrylic acidor a mixture of methacrylic acid and at least one furthermonoethylenically unsaturated carboxylic acid.

In particular, c) is methacrylic acid or a mixture of methacrylic acidand acrylic acid.

In a preferred embodiment of the invention, the weight ratio ofmethacrylic acid to the at least one further monoethylenicallyunsaturated carboxylic acid is at least greater than 1, preferablygreater than 2, particularly preferably greater than 3.

Component d)

The copolymers according to the invention are obtainable by free-radicalpolymerization of a monomer mixture M which comprises, as component d),0.1 to 30% by weight of at least one compound with a free-radicallypolymerizable α,β-ethylenically unsaturated double bond and at least onecationogenic and/or cationic group per molecule.

The cationogenic or cationic groups of component d) are preferablynitrogen-containing groups, such as primary, secondary and tertiaryamino groups, and quaternary ammonium groups. The nitrogen-containinggroups are preferably tertiary amino groups. Preference is given tousing the compounds d) in uncharged form for the polymerization.However, use in charged form is also suitable. Charged cationic groupscan be produced, for example, from the amine nitrogens by protonation,e.g. with monobasic or polybasic carboxylic acids, such as lactic acidor tartaric acid, or mineral acids, such as phosphoric acid, sulfuricacid and hydrochloric acid.

Preferably, component d) is chosen from

-   d1) esters of α,β-ethylenically unsaturated mono- and dicarboxylic    acids with amino alcohols which may be mono- or dialkylated on the    amine nitrogen,-   d2) amides of α,β-ethylenically unsaturated mono- and dicarboxylic    acids with diamines which have at least one primary or secondary    amino group,-   d3) N,N-diallylamine,-   d4) N,N-diallyl-N-alkylamines and derivatives thereof,-   d5) vinyl- and allyl-substituted nitrogen heterocycles,-   d6) vinyl- and allyl-substituted heteroaromatic compounds and    mixtures thereof.

Suitable compounds d) are d1) the esters of α,β-ethylenicallyunsaturated mono- and dicarboxylic acids with aminoalcohols. Preferredaminoalcohols are C₂-C₁₂-aminoalcohols which are C₁-C₈-mono- ordialkylated on the amine nitrogen. Suitable acid components of theseesters are, for example, acrylic acid, methacrylic acid, fumaric acid,maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutylmaleate and mixtures thereof. Preference is given to using acrylic acid,methacrylic acid or mixtures thereof. Particularly preferred compoundsd) are N-methylaminoethyl (meth)acrylate, N-ethylaminoethyl(meth)acrylate, N-(n-propyl)aminoethyl (meth)acrylate,N-(n-butyl)aminoethyl (meth)acrylate, N-(tert-butyl)aminoethyl(meth)acrylate, N,N-dimethylaminomethyl (meth)acrylate,N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate,N,N-diethylaminopropyl (meth)acrylate and N,N-dimethylaminocyclohexyl(meth)acrylate. In particular, N-(tert-butyl)aminoethyl acrylate andN-(tert-butyl)aminoethyl methacrylate are used as compound d).

Suitable monomers d) are also d2) the amides of the abovementionedα,β-ethylenically unsaturated mono- and dicarboxylic acids with diamineswhich have at least one primary or secondary amino group. Preference isgiven to diamines which have one tertiary and one primary or secondaryamino group. As monomers e), preference is given to usingN-[2-(dimethylamino)ethyl]acrylamide,N-[2-(dimethylamino)ethyl]methacrylamide,N-[3-(dimethylamino)propyl]acrylamide,N-[3-(dimethylamino)propyl]methacrylamide,N-[4-(dimethylamino)butyl]acrylamide,N-[4-(dimethylamino)butyl]methacrylamide,N-[2-(diethylamino)ethyl]acrylamide,N-[4-(dimethylamino)cyclohexyl]-acrylamide andN-[4-(dimethylamino)cyclohexyl]methacrylamide. Particular preference isgiven to using N-[3-(dimethylamino)propyl]acrylamide and/orN-[3-(dimethylamino)propyl]methacrylamide.

Suitable monomers d) are also d3) N,N-diallylamines and d4)N,N-diallyl-N-alkylamines and acid addition salts thereof. Alkyl here ispreferably C₁-C₂₄-alkyl. Preference is given, for example, toN,N-diallyl-N-methylamine.

Suitable monomers d) are also d5) vinyl- and allyl-substituted nitrogenheterocycles, such as N-vinylimidazole, N-vinylimidazole derivatives,e.g. N-vinyl-2-methylimidazole, vinyl- and allyl-substitutedheteroaromatic compounds, such as 2- and 4-vinylpyridine, 2- and4-allylpyridine, and the salts thereof.

Suitable monomers d) are also N-vinylimidazoles of the general formula(II) in which R¹ to R³ is hydrogen, C₁-C₄-alkyl or phenyl

Examples of compounds of the general formula (II) are given in Table 1below: TABLE 1 R¹ R² R³ H H H Me H H H Me H H H Me Me Me H H Me Me Me HMe Ph H H H Ph H H H Ph Ph Me H Ph H Me Me Ph H H Ph Me H Me Ph Me H PhMe = methylPh = phenyl

Particular preference is given to the compounds of component d) chosenfrom N-(tert-butylamino)ethyl (meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N-[3-(dimethylamino)propyl](meth)acrylamide,vinylimidazole and mixtures thereof.

The copolymers according to the invention comprise at least 0.1% byweight, preferably at least 1% by weight, particularly preferably atleast 2% by weight and in particular at least 3% by weight and at most30% by weight, preferably at most 20% by weight, particularly preferablyat most 15% by weight and in particular at most 10% by weight, ofmonomer d), based on the total weight of the monomers used for thepolymerization, in copolymerized form.

A preferred embodiment of the invention is copolymers obtainable byfree-radical polymerization of a monomer mixture M comprising

-   30 to 70% by weight of component a),-   10 to 40% by weight of component b),-   10 to 25% by weight of component c),-   0.5 to 6% by weight of component d).

A further preferred embodiment of the invention is copolymers obtainableby free-radical polymerization of a monomer mixture M comprising

-   50 to 80% by weight of component a),-   0% by weight of component b),-   15 to 35% by weight of component c),-   0.5 to 12% by weight of component d).

The copolymers according to the invention can additionally comprise, incopolymerized form, at least one monomer e) different from components a)to d) and copolymerizable therewith.

Component e) is preferably chosen from esters of α,β-ethylenicallyunsaturated mono- and dicarboxylic acids with C₁-C₃₀-alkanols andC₁-C₃₀-alkanediols, amides of α,β-ethylenicallyunsaturated mono- anddicarboxylic acids with C₂-C₃₀-aminoalcohols which have a primary orsecondary amino group, N-vinylamides of saturated monocarboxylic acids,primary amides of α,β-ethylenically unsaturated monocarboxylic acids andN-alkyl and N,N-dialkyl derivatives thereof, esters of vinyl alcohol andallyl alcohol with C₁-C₃₀-monocarboxylic acids, vinyl ethers, vinylaromatics, vinyl halides, vinylidene halides, C₁-C₈-monoolefins,nonaromatic hydrocarbons with at least two conjugated double bonds andmixtures thereof.

N-vinylamide compounds suitable as monomers e) are, for example,N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide,N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide,N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide.In a preferred embodiment, the copolymers according to the inventioncomprise no N-vinylamide compounds in copolymerized form.

Suitable additional monomers e) are also 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropylacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutylmethacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate,6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate,3-hydroxy-2-ethylhexyl acrylate and 3-hydroxy-2-ethylhexyl methacrylate.

Suitable additional monomers e) are also 2-hydroxyethylacrylamide,

-   2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide,-   2-hydroxypropylacrylamide, 2-hydroxypropylmethacrylamide,-   3-hydroxypropylacrylamide, 3-hydroxypropylmethacrylamide,-   3-hydroxybutylacrylamide, 3-hydroxybutylmethacrylamide,    4-hydroxybutylacrylamide,-   4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide,-   6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide and    3-hydroxy-2-ethylhexylmethacrylamide.

Suitable monomers e) are also polyether acrylates, which, for thepurposes of this invention, are generally understood as meaning estersof α,β-ethylenically unsaturated mono- and dicarboxylic acids withpolyetherols. Suitable polyetherols are linear or branched substanceshaving terminal hydroxyl groups and comprising ether bonds. In general,they have a molecular weight in the range from about 150 to 20 000.Suitable polyetherols are polyalkylene glycols, such as polyethyleneglycols, polypropylene glycols, polytetrahydrofurans and alkylene oxidecopolymers. Suitable alkylene oxides for preparing alkylene oxidecopolymers are, for example, ethylene oxide, propylene oxide,epichlorohydrin, 1,2- and 2,3-butylene oxide. The alkylene oxidecopolymers can comprise the copolymerized alkylene oxide units in randomdistribution or in the form of blocks. Preference is given to ethyleneoxide/propylene oxide copolymers.

As component e), preference is given to polyether acrylates of thegeneral formula III

in whichthe order of the alkylene oxide units is arbitrary,

-   k and l, independently of one another, are an integer from 0 to    1000, the sum of k and l being at least 5,-   R⁴ is hydrogen, C₁-C₃₀-alkyl or C₅-C₈-cycloalkyl,-   R⁵ is hydrogen or C₁-C₈-alkyl,-   Y² is O or NR⁶, where R⁶ is hydrogen, C₁-C₃₀-alkyl or    C₅-C₈-cycloalkyl.

Preferably, k is an integer from 1 to 500, in particular 3 to 250.Preferably, l is an integer from 0 to 100.

Preferably, R⁵ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular hydrogen,methyl or ethyl.

Preferably, R⁴ in the formula II is hydrogen, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl,decyl, lauryl, palmityl or stearyl.

Preferably, Y² in the formula III is O or NH.

Suitable polyetheracrylates e) are, for example, the polycondensationproducts of the abovementioned α,β-ethylenically unsaturated mono-and/or dicarboxylic acids and the acid chlorides, amides and anhydridesthereof with polyetherols. Suitable polyetherols can be prepared easilyby reacting ethylene oxide, 1,2-propylene oxide and/or epichlorohydrinwith a starter molecule, such as water or a short-chain alcohol R⁴—OH.The alkylene oxides can be used individually, alternately one after theother or as a mixture. The polyether acrylates e) can be used on theirown or in mixtures for preparing the polymers used according to theinvention.

Suitable additional monomers e) are the esters of α,β-ethylenicallyunsaturated mono- and dicarboxylic acids different from component a),such as, for example, methyl (meth)acrylate, ethyl acrylate, methylethacrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-propylethacrylate, ethyl ethacrylate, isopropyl ethacrylate, n-butyl(meth)acrylate, n-butyl ethacrylate, tert-butyl (meth)acrylate,tert-butyl ethacrylate, isobutyl (meth)acrylate, isobutyl ethacrylate,sec-butyl (meth)acrylate, butyl ethacrylate, 2-pentyl (meth)acrylate,3-pentyl (meth)acrylate, isopentyl acrylate, neopentyl acrylate, n-octyl(meth)acrylate, 1,1,3,3-tetramethylbutyl (meth)acrylate, ethylhexyl(meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate,n-undecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl(meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate,heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, arrachinyl(meth)acrylate, behenyl (meth)acrylate, lignocerenyl (meth)acrylate,cerotinyl (meth)acrylate, melissinyl (meth)acrylate, palmitoleinyl(meth)acrylate, oleyl (meth)acrylate, linolyl (meth)acrylate, linolenyl(meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate,phenoxyethyl acrylate, t-butylcyclohexyl acrylate, cyclohexyl(meth)acrylate, ureido (meth)acrylate, tetrahydrofurfuryl (meth)acrylateand mixtures thereof.

Preferred monomers e) are the esters of α,β-ethylenically unsaturatedmono- and dicarboxylic acids with C₁-C₄-alkanols.

Suitable additional monomers e) are also N-(n-butyl)methacrylamide,N-(sec-butyl)methacrylamide, N-(tert-butyl)methacrylamide,N-(n-pentyl)(meth)acrylamide, N-(n-hexyl)(meth)acrylamide,N-(n-heptyl)(meth)acrylamide, N-(n-octyl)(meth)acrylamide,N-(tert-octyl)(meth)acrylamide,N-(1,1,3,3-tetramethylbutyl)(meth)acrylamide,N-ethylhexyl(meth)acrylamide, N-(n-nonyl)(meth)acrylamide,N-(n-decyl)(meth)acrylamide, N-(n-undecyl)(meth)acrylamide,N-tridecyl(meth)acrylamide, N-myristyl(meth)acrylamide,N-pentadecyl(meth)acrylamide, N-palmityl(meth)acrylamide,N-heptadecyl(meth)acrylamide, N-nonadecyl(meth)acrylamide,N-arrachinyl(meth)acrylamide, N-behenyl(meth)acrylamide,N-lignocerenyl(meth)acrylamide, N-cerotinyl(meth)acrylamide,N-melissinyl(meth)acrylamide, N-palmitoleinyl(meth)acrylamide,N-oleyl(meth)acrylamide, N-linolyl(meth)acrylamide,N-linolenyl(meth)acrylamide, N-stearyl(meth)acrylamide,N-lauryl(meth)acrylamide.

Suitable additional monomers e) are also vinyl acetate, vinylpropionate, vinyl butyrate and mixtures thereof.

Suitable additional monomers e) are also ethylene, propylene,isobutylene, butadiene, styrene, α-methylstyrene, acrylonitrile,methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride,vinylidene fluoride and mixtures thereof.

The abovementioned additional monomers e) can be used individually or inthe form of any desired mixtures.

The copolymers according to the invention comprise at most 10% byweight, particularly preferably at most 7% by weight, in particular atmost 5% by weight, based on the total weight of the monomers used forthe polymerization, of at least one monomer e) in copolymerized form.

If a monomer e) is used, then it is preferably in an amount of at least0.5% by weight, particularly preferably at least 2% by weight and inparticular at least 3% by weight.

Crosslinker f)

If desired, the copolymers according to the invention can comprise atleast one crosslinker, i.e. a compound with two or more than twoethylenically unsaturated, nonconjugated double bonds in copolymerizedform.

Preferably, crosslinkers are used in an amount of from 0.01 to 3% byweight, particularly preferably 0.1 to 2% by weight, based on the totalweight of the monomers used for the polymerization.

Suitable crosslinkers f) are, for example, acrylic esters, methacrylicesters, allyl ethers or vinyl ethers of at least dihydric alcohols. TheOH groups of the parent alcohols may here be completely or partiallyetherified or esterified; however, the crosslinkers comprise at leasttwo ethylenically unsaturated groups.

Examples of the parent alcohols are dihydric alcohols, such as1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-ene-1,4-diol,1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol,1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl glycol,3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol,2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexane, hydroxypivalicneopentyl glycol monoester, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis[4-(2-hydroxypropyl)phenyl]propane, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol, andpolyethylene glycols, polypropylene glycols and polytetrahydrofuranswith molecular weights of in each case from 200 to 10 000. Apart fromthe homopolymers of ethylene oxide and/or propylene oxide it is alsopossible to use block copolymers of ethylene oxide or propylene oxide orcopolymers which comprise ethylene oxide and propylene oxide groups inincorporated form. Examples of parent alcohols with more than two OHgroups are trimethylolpropane, glycerol, pentaerythritol,1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan,sugars, such as sucrose, glucose, mannose. The polyhydric alcohols canof course also be used following reaction with ethylene oxide orpropylene oxide as the corresponding ethoxylates or propoxylates,respectively. The polyhydric alcohols can also firstly be converted tothe corresponding glycidyl ethers by reaction with epichlorohydrin.

Further suitable crosslinkers f) are the vinyl esters or the esters ofmonohydric, unsaturated alcohols with ethylenically unsaturatedC₃-C₆-carboxylic acids, for example acrylic acid, methacrylic acid,itaconic acid, maleic acid or fumaric acid. Examples of such alcoholsare allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol,9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamylalcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. It is,however, also possible to esterify the monohydric unsaturated alcoholswith polybasic carboxylic acids, for example malonic acid, tartaricacid, trimellitic acid, phthalic acid, terephthalic acid, citric acid orsuccinic acid.

Further suitable crosslinkers f) are esters of unsaturated carboxylicacids with the above-described polyhydric alcohols, for example of oleicacid, crotonic acid, cinnamic acid or 10-undecenoic acid.

Further suitable crosslinkers f) are urethane diacrylates and urethanepolyacrylates, as are commercially available, for example, under thename Laromer®.

Suitable crosslinkers f) are also straight-chain or branched, linear orcyclic, aliphatic or aromatic hydrocarbons which have at least twodouble bonds which, in the case of aliphatic hydrocarbons, must not beconjugated, e.g. divinylbenzene, divinyltoluene, 1,7-octadiene,1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane orpolybutadienes with molecular weights of from 200 to 20 000.

Further suitable crosslinkers f) are the acrylamides, methacrylamidesand N-allylamines of at least difunctional amines. Such amines are, forexample, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane,1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine,diethylenetriamine or isophoronediamine. Likewise suitable are theamides of allylamine and unsaturated carboxylic acids, such as acrylicacid, methacrylic acid, itaconic acid, maleic acid, or at least dibasiccarboxylic acids as have been described above.

Triallylamine and triallylmonoalkylammonium salts, e.g.triallylmethylammonium chloride or methylsulfate, are also suitablecrosslinkers f).

Also suitable are N-vinyl compounds of urea derivatives, at leastdifunctional amides, cyanurates or urethanes, for example of urea,ethyleneurea, propyleneurea or tartramide, e.g. N,N′-divinylethyleneureaor N,N′-divinylpropyleneurea.

Further suitable crosslinkers f) are divinyidioxane, tetraallylsilane ortetravinylsilane.

It is of course also possible to use mixtures of the abovementionedcompounds f). Preference is given to using water-soluble crosslinkersf).

Crosslinkers f) used particularly preferably are, for example,methylenebisacrylamide, triallylamine and triallylalkylammonium salts,divinylimidazole, pentaerythritol triallyl ether,N,N′-divinylethyleneurea, reaction products of polyhydric alcohols withacrylic acid or methacrylic acid, methacrylic esters and acrylic estersof polyalkylene oxides or polyhydric alcohols which have been reactedwith ethylene oxide and/or propylene oxide and/or epichlorohydrin.

Very particularly preferred crosslinkers f) are pentaerythritol triallylether, methylenebisacrylamide, N,N′-divinylethyleneurea, triallylamineand triallylmonoalkylammonium salts and acrylic esters of glycol,butanediol, trimethylolpropane or glycerol or acrylic esters of glycol,butanediol, trimethylolpropane or glycerol reacted with ethylene oxideand/or epichlorohydrin.

In a preferred embodiment, copolymers according to the invention areobtainable by free-radical polymerization of a) ethyl methacrylate, b)N-vinylpyrrolidone or N-vinylcaprolactam or mixtures thereof, c)methacrylic acid or a mixture of methacrylic acid and acrylic acid andcomponent d) chosen from the group consisting ofN-[3-(dimethylamino)propyl](meth)acrylamide, N-(tert-butyl)aminoethylmethacrylate, vinylimidazole and mixtures thereof.

Preparation of the Copolymers

The copolymers according to the invention can be prepared, for example,by solution, precipitation, suspension or emulsion polymerization. Suchprocesses are known in principle to the person skilled in the art.Preference is given to preparation by solution polymerization.

Preferred solvents for the polymerization are aqueous solvents, such aswater and mixtures of water with water-miscible solvents, for examplealcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol,sec-butanol, tert-butanol, n-hexanol and cyclohexanol, and glycols, suchas ethylene glycol, propylene glycol and butylene glycol, and the methylor ethyl ethers of dihydric alcohols, diethylene glycol, triethyleneglycol, polyethylene glycols with number-average molecular weights up toabout 3000, glycerol and dioxane.

The polymerization is particularly preferably in water or awater/alcohol mixture, for example in a water/ethanol mixture.

The polymerization can in principle be carried out at the pH resultingfrom the monomers used. If at least one N-vinyllactam is used for thepolymerization (=component b)), then the pH of the polymerization mediumis preferably adjusted to a value of from 5 to 8, preferably 6.5 to 7.5.It is advantagoues to then keep the pH in this range throughout thepolymerization. Of suitability for adjusting the pH before, during orafter the polymerization are, in principle, all inorganic or organicbases (and if appropriate acids), in particular those which, apart froma possible salt formation, do not undergo reaction with the monomers.Suitable bases are, for example, alkali metal and alkaline earth metalhydroxides, ammonia, and primary, secondary and tertiary amines, such astriethylamine, and aminoalcohols, such as triethanolamine,methyldiethanolamine, dimethylethanolamine or 2-amino-2-methylpropanol.For adjusting the pH, preference is given to using at least one tertiaryamine, which is chosen in particular from N,N-dimethylethanolamine,N-methyldiethanolamine, triethanolamine and mixtures thereof. If, forthe polymerization, at least one N-vinyllactam is used (=component b)),then the pH of the polymerization medium is preferably adjusted usingN,N-dimethylethanolamine.

The polymerization temperatures are preferably in a range from about 30to 120° C., particularly preferably 40 to 100° C. The polymerization isusually carried out under atmospheric pressure, although it can alsoproceed under reduced or elevated pressure. A suitable pressure range isbetween 1 and 5 bar.

For the copolymerization, the monomers can be polymerized usinginitiators which form free radicals.

Initiators for the free-radical polymerization which may be used hereare the peroxo and/or azo compounds customary for this purpose, forexample alkali metal or ammonium peroxidisulfates, diacetyl peroxide,dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide,tert-butyl perbenzoate, tert-butyl perpivalate, tert-butylperoxy-2-ethylhexanoate, tert-butyl permaleate, cumene hydroperoxide,diisopropyl peroxidicarbamate, bis-(o-toloyl) peroxide, didecanoylperoxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butylperisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butylhydroperoxide, azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane)hydrochloride (V50 from Wako Pure Chemicals Industries, Ltd.), or2,2′-azobis(2-methylbutyronitrile). Also suitable are initiator mixturesor redox initiator systems, such as, for example, ascorbic acid/iron(II)sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodiumdisulfite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate,H₂O₂/Cu^(I).

To adjust the molecular weight, the polymerization can be carried out inthe presence of at least one regulator. Regulators which may be used arethe customary compounds known to the person skilled in the art, such as,for example, sulfur compounds, e.g. mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid or dodecylmercaptan, andtribromochloromethane or other compounds which have a regulating effecton the molecular weight of the resulting polymers. A preferred regulatoris cysteine.

To achieve the purest possible polymers with a low residual monomercontent, the polymerization (main polymerization) can be followed by anafter-polymerization step. The after-polymerization can take place inthe presence of the same initiator system as the main polymerization ora different initiator system. Preferably, the after-polymerization iscarried out at least at the same temperature as the main polymerization,preferably at a higher temperature. If desired, the reaction mixture canbe subjected to stripping with steam or to steam distillation followingthe polymerization or between the first and the second polymerizationsteps.

If, in the preparation of the polymers, an organic solvent is used, thenthis can be removed by customary processes known to the person skilledin the art, e.g. by distillation at reduced pressure.

If the monomer mixture M comprises N-vinyllactams (component b)), thenit is advantageous, during the polymerization, to set the pH to a valuein the range 5 to 8, preferably 6.5 to 7.5 and, after the polymerizationhas finished, to set the pH to a value in the range from 5 to 7,preferably 5.5 to 6.5 and then to carry out steam distillation of thepolymerization solution.

The invention thus further provides a method of producing the copolymersaccording to the invention comprising the steps

-   1) free-radical polymerization of the monomer mixture M comprising    the components a), b), c), d) and if appropriate e) at a pH in the    range from 5 to 8, preferably 6.5 to 7.5,-   2) adjustment of the pH when polymerization is complete to a value    in the range from 5 to 7, preferably 5.5 to 6.5,-   3) steam distillation of the polymerization solution,-   4) if appropriate adjustment of the pH of the distilled    polymerization solution to a value in the range from 7.5 to 9.0,    preferably 8.0 to 8.5 after the steam distillation.

The polymerization is regarded as being complete if the fraction ofunpolymerized monomers (=residual monomers) in the polymerizationsolution is at most 1% by weight, preferably at most 0.1% by weight,particularly preferably at most 0.01% by weight, based on the totalweight of the monomers used for the polymerization.

Neutralization

Moreover, the present polymers can be partially or completelyneutralized. For using the polymers in hair cosmetic preparations inparticular, partial or complete neutralization is advantageous. Inpreferred embodiments, the polymers are neutralized for example to atleast 10%, preferably at least 30%, further preferably to at least 40%,particularly preferably to at least 50%, very particularly preferably toat least 70% and especially to at least 95%.

In a very particularly preferred embodiment, the polymers areneutralized to at least 99%. Most preferably, the neutralization is toat least 100%.

It is also advantageous if the neutralizing agent is added in more thanan equivalent amount, equivalent amount being understood as meaning theamount which is required to neutralize all of the neutralizable groupsof the polymers.

The neutralization can also take place with

-   -   a mono-, di- or trialkanolamine with 2 to 5 carbon atoms in the        alkanol radical which, if appropriate, is in etherified form,        for example mono-, di- and triethanolamine, mono-, di- and        tri-n-propanolamine, mono-, di- and triisopropanolamine,        2-amino-2-methylpropanol and di(2-methoxyethyl)amine,    -   an alkanediolamine with 2 to 5 carbon atoms, for example        2-amino-2-methylpropane-1,3-diol and        2-amino-2-ethylpropane-1,3-diol, or    -   a primary, secondary or tertiary alkylamine with a total of 5 to        10 carbon atoms, for example N,N-diethylpropylamine or        3-diethylamino-1-propylamine.

Suitable alkali metal hydroxides for the neutralization are primarilysodium hydroxide or potassium hydroxide and ammonium hydroxide.

Good neutralization results are often obtained with2-amino-2-methylpropanol, triisopropanolamine,2-amino-2-ethylpropane-1,3-diol, N,N-dimethylaminoethanol or3-diethylamino-1-propylamine.

Suitable for neutralizing the polymers in the preparations andcompositions according to the invention are, in particular, siliconepolymers comprising amino groups. Suitable silicone polymers comprisingamino groups are, for example, the silicone-aminopolyalkylene oxideblock copolymers of WO 97/32917, the products Silsoft®A-843 (DimethiconeBisamino Hydroxypropyl Copolyol) and Silsoft®A-858 (TrimethylsilylAmodimethicone Copolymer) (both Witco). Further suitable are also theneutralization polymers of EP-A 1035144 and in particular thesilicone-containing neutralization polymers according to claim 12 ofEP-A 1035144.

Drying

The liquid polymer compositions obtained can be converted to powder formby various drying methods, such as, for example, spray drying, fluidizedspray drying, drum drying or freeze drying. Preference is given to usingspray drying. The dry polymer powders obtained in this way canadvantageously be converted again to an aqueous solution or dispersionby dissolution or redispersion, respectively, in water. Pulverulentcopolymers have the advantage of better storability, simplertransportation option and generally exhibit a lower propensity formicrobial attack.

Cosmetic and Pharmaceutical Compositions

The copolymers described above are exceptionally suitable for preparingcosmetic and pharmaceutical compositions. They serve here, for example,as polymeric film formers in preparations for bodycare, which includesapplication in cosmetic preparations for keratinous surfaces such asskin, hair, nails, and also mouthcare preparations. They can be used andformulated universally into a very wide range of cosmetic preparationsand are compatible with the customary components. In particular, thecopolymers according to the invention are suitable for preparing haircosmetic compositions. Compared with customary polymers known from theprior art, they are advantageously suitable for creating elastichairstyles coupled with strong hold (even at high atmospheric humidity).The copolymers according to the invention are also characterized by goodpropellant gas compatibility, good solubility in water oraqueous/alcoholic solvent mixtures, suitability for use in low-VOCformulations and good ability to be washed out. In addition, theyusually also have good conditioning properties, i.e. they improve hairtreated therewith in its sensory properties, such as feel, volume,handability etc. Hairspray formulations based on the copolymersaccording to the invention are characterized by good rheologicalproperties and good sprayability.

Cosmetically or Pharmaceutically Acceptable Carrier B)

The compositions according to the invention have a cosmetically orpharmaceutically acceptable carrier B) which is chosen from

-   i) water,-   ii) water-miscible organic solvents, preferably C₂-C₄-alkanols, in    particular ethanol,-   iii) oils, fats, waxes,-   iv) esters of C₆-C₃₀-monocarboxylic acids with mono-, di- or    trihydric alcohols which are different from iii),-   v) saturated acyclic and cyclic hydrocarbons,-   vi) fatty acids,-   vii) fatty alcohols,-   viii) propellant gases and mixtures thereof.

The compositions according to the invention have, for example, an oil orfat component B) which is chosen from: hydrocarbons of low polarity,such as mineral oils; linear saturated hydrocarbons, preferably withmore than 8 carbon atoms, such as tetradecane, hexadecane, octadecaneetc.; cyclic hydrocarbons, such as decahydronaphthalene; branchedhydrocarbons; animal and vegetable oils; waxes; wax esters; vaseline;esters, preferably esters of fatty acids, such as, for example, theesters of C₁-C₂₄-monoalcohols with C₁-C₂₂-monocarboxylic acids, such asisopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propylpalmitate, isopropyl palmitate, hexacosanyl palmitate, octacosanylpalmitate, triacontanyl palmitate, dotriacontanyl palmitate,tetratriacontanyl palmitate, hexacosanyl stearate, octacosanyl stearate,triacontanyl stearate, dotriacontanyl stearate, tetratriacontanylstearate; salicylates, such as C₁-C₁₀-salicylates, e.g. octylsalicylate; benzoate esters, such as C₁₀-C₁₅-alkyl benzoates, benzylbenzoate; other cosmetic esters, such as fatty acid triglycerides,propylene glycol monolaurate, polyethylene glycol monolaurate,C₁₀-C₁₅-alkyl lactates, etc. and mixtures thereof.

Suitable silicone oils B) are, for example, linearpolydimethylsiloxanes, poly(methylphenylsiloxanes), cyclic siloxanes andmixtures thereof. The number-average molecular weight of thepolydimethylsiloxanes and poly(methylphenylsiloxanes) is preferably in arange from about 1000 to 150 000 g/mol. Preferred cyclic siloxanes have4- to 8-membered rings. Suitable cyclic siloxanes are commerciallyavailable, for example, under the name cyclomethicone.

Preferred oil or fat components B) are chosen from paraffin and paraffinoils; vaseline; natural fats and oils, such as castor oil, soya oil,peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoabutter, almond oil, peach kernel oil, ricinus oil, cod-liver oil, porklard, spermaceti, spermaceti oil, sperm oil, wheatgerm oil, macadamianut oil, evening primrose oil, jojoba oil; fatty alcohols, such aslauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleylalcohol, cetyl alcohol; fatty acids, such as myristic acid, stearicacid, palmitic acid, oleic acid, linoleic acid, linolenic acid andsaturated, unsaturated and substituted fatty acids, different therefrom;waxes, such as beeswax, carnauba wax, candililla wax, spermaceti, andmixtures of the abovementioned oil and fat components.

Suitable cosmetically and pharmaceutically compatible oil and fatcomponents B) are described in Karl-Heinz Schrader, Grundlagen undRezepturen der Kosmetika [Fundamentals and formulations of cosmetics],2^(nd) edition, Verlag Hüthig, Heidelberg, pp. 319-355, to whichreference is hereby made.

Suitable hydrophilic carriers B) are chosen from water, 1-, 2- orpolyhydric alcohols having preferably 1 to 8 carbon atoms, such asethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol,etc.

The cosmetic compositions according to the invention may be skincosmetic, hair cosmetic, dermatological, hygiene or pharmaceuticalcompositions. On account of their film-forming properties, thecopolymers described above are suitable in particular as additives forhair and skin cosmetics.

Preferably, the compositions according to the invention are in the formof a spray, gel, foam, an ointment, cream, emulsion, suspension, lotion,milk or paste. If desired, liposomes or microspheres can also be used.

In a preferred embodiment of the invention, the compositions have acontent of volatile organic components of at most 80% by weight,preferably at most 55% by weight and in particular at most 30% byweight. A preferred subject-matter is thus compositions which correspondto the low-VOC standard, i.e. VOC-80 and VOC-55 standard.

The cosmetically or pharmaceutically active compositions according tothe invention can additionally comprise cosmetically and/ordermatologically active ingredients and auxiliaries.

Preferably, the cosmetic compositions according to the inventioncomprise at least one copolymer as defined above (=component A), atleast one carrier B) as defined above and at least one constituentdifferent therefrom which is chosen from cosmetically activeingredients, emulsifiers, surfactants, preservatives, perfume oils,thickeners, hair polymers, hair and skin conditioners, graft polymers,water-soluble or dispersible silicone-containing polymers,photoprotective agents, bleaches, gel formers, care agents, colorants,tinting agents, tanning agents, dyes, pigments, bodying agents,humectants, regreasing agents, collagen, protein hydrolyzates, lipids,antioxidants, antifoams, antistats, emollients and softeners.

Thickeners

Customary thickeners in such formulations are crosslinked polyacrylicacids and derivatives thereof, polysaccharides and derivatives thereof,such as xanthan gum, agar agar, alginates or tyloses, cellulosederivatives, e.g. carboxymethylcellulose orhydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fattyacids, polyvinyl alcohol and polyvinylpyrrolidone. Preference is givento using nonionic thickeners.

Cosmetically and/or Dermatologically Active Ingredients

Suitable cosmetically and/or dermatologically active ingredients are,for example, coloring active ingredients, skin and hair pigmentationagents, tinting agents, tanning agents, bleaches, keratin-hardeningsubstances, antimicrobial active ingredients, photofilter activeingredients, repellent active ingredients, hyperemic substances,keratolytic and keratoplastic substances, antidandruff activeingredients, antiphlogistics, keratinising substances, antioxidativeactive ingredients and active ingredients acting as free-radicalscavengers, skin moisturizing or humectant substances, regreasing activeingredients, antierythematous or antiallergic active ingredients andmixtures thereof.

Artificially skin-tanning active ingredients which are suitable fortanning the skin without natural or artificial exposure to UV rays are,for example, dihydroxyacetone, alloxan and walnut shell extract.Suitable keratin-hardening substances are generally active ingredientsas are also used in antiperspirants, such as, for example, potassiumaluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.Antimicrobial active ingredients are used for destroying microorganismsand/or for inhibiting their growth and thus serve both as preservativeand also as deodorizing substance which reduces the formation or theintensity of body odor. These include, for example, customarypreservatives known to the person skilled in the art, such asp-hydroxybenzoic esters, imidazolidinyl urea, formaldehyde, sorbic acid,benzoic acid, salicylic acid, etc. Such deodorizing substances are, forexample, zinc ricinoleate, triclosan, undecylenic acid alkylolamides,triethyl citrate, chlorhexidine etc.

Suitable photofilter active ingredients are substances which absorb UVrays in the UV-B and/or UV-A region. Suitable UV filters are, forexample, 2,4,6-triaryl-1,3,5-triazines in which the aryl groups can ineach case carry at least one substituent which is preferably chosen fromhydroxy, alkoxy, specifically methoxy, alkoxycarbonyl, specificallymethoxycarbonyl and ethoxycarbonyl and mixtures thereof. Also suitableare p-aminobenzoic esters, cinnamic esters, benzophenones, camphorderivatives, and pigments which deter UV rays, such as titanium dioxide,talc and zinc oxide.

Examples of UV Photoprotective Filters are: No. Substance CAS No. 14-Aminobenzoic acid   150-13-0 23-(4′-Trimethylammonium)benzylidenebornan-2-one  52793-97-2methylsulfate 3 3,3,5-Trimethylcyclohexyl salicylate (homosalate)  118-56-9 4 2-Hydroxy-4-methoxybenzophenone (oxybenzone)   131-57-7 52-Phenylbenzimidazole-5-sulfonic acid and its  27503-81-7 potassium,sodium and triethanolamine salts 63,3′-(1,4-Phenylenedimethine)bis(7,7-dimethyl-2-  90457-82-2oxobicyclo[2.2.1]heptane-1-methanesulfonic acid) and its salts 7Polyethoxyethyl 4-bis(polyethoxy)aminobenzoate 113010-52-9 82-Ethylhexyl 4-dimethylaminobenzoate  21245-02-3 9 2-Ethylhexylsalicylate   118-60-5 10 2-Isoamyl 4-methoxycinnamate  71617-10-2 112-Ethylhexyl 4-methoxycinnamate  5466-77-3 122-Hydroxy-4-methoxybenzophenone-5-sulfonic acid  4065-45-6(sulisobenzone) and the sodium salt 133-(4′-Sulfo)benzylidene-bornan-2-one and salts  58030-58-6 143-Benzylidenebornan-2-one  16087-24-8 151-(4′-Isopropylphenyl)-3-phenylpropane-1,3-dione  63260-25-9 164-Isopropylbenzyl salicylate  94134-93-7 172,4,6-Trianiline-(o-carbo-2′-ethylhexyl-  88122-99-01′-oxy)-1,3,5-triazine 18 3-Imidazol-4-ylacrylic acid and its ethylester   104-98-3 19 Menthyl o-aminobenzoate or: 5-methyl-   134-09-82-(1-methylethyl)2-aminobenzoate 20 Glyceryl p-aminobenzoate or1-glyceryl   136-44-7 4-aminobenzoate 212,2′-Dihydroxy-4-methoxybenzophenone   131-53-3 (dioxybenzone) 222-Hydroxy-4-methoxy-4-methylbenzophenone  1641-17-4 (mexenone) 23Triethanolamine salicylate  2174-16-5 24 Dimethoxyphenylglyoxalic acidor: sodium 3,4-  4732-70-1 dimethoxyphenylglyoxalate 253-(4′Sulfo)benzylidenebornan-2-one and its salts  56039-58-8 262,2′,4,4′-Tetrahydroxybenzophenone   131-55-5 272,2′-Methylenebis[6(2H-benzotriazol-2-yl)- 103597-4514-(1,1,3,3,-tetramethylbutyl)phenol] 282,2′-(1,4-Phenylene)-bis-1H-benzimidazole- 180898-37-7 4,6-disulfonicacid, Na salt 29 2,4-bis-[4-(2-Ethylhexyloxy)-2-hydroxy] 187393-00-6phenyl-6-(4-methoxyphenyl)-(1,3,5)-triazine 303-(4-Methylbenzylidene)camphor  36861-47-9 31 Polyethoxyethyl4-bis(polyethoxy) 113010-52-9 paraaminobenzoate 322,4-Dihydroxybenzophenone   131-56-6 332,2′-Dihydroxy-4,4′-dimethoxybenzophenone 5,  3121-60-6 5′-disodiumsulfonate

Further combinable photoprotective agents are, inter alia, the followingcompounds:

Also suitable are pigments which deter UV rays, such as titaniumdioxide, talc and zinc oxide.

Photoprotective agents suitable for use in the preparations according tothe invention are also the compounds specified in EP-A 1 084 696 inparagraphs [0036] to [0053], the entire contents of which are herebyincorporated by reference.

The list of specified UV photoprotective filters which can be used inthe preparations according to the invention is not of course intended tobe limiting.

Antimicrobial Agents

In addition, antimicrobial agents can also be used in the preparationsaccording to the invention. In general, these include all suitablepreservatives with a specific action against Gram-positive bacteria,e.g. triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether),chlorhexidine (1,1′-hexamethylenebis[5-(4-chlorophenyl)biguanide) andTTC (3,4,4′-trichlorocarbanilide).

Quarternary ammonium compounds are in principle likewise suitable, butare preferably used for disinfecting soaps and washing lotions.

Numerous fragrances also have antimicrobial properties. Specialcombinations with particular effectiveness toward Gram-positive bacteriaare used for the composition of so-called deodorant perfumes.

A large number of essential oils or their characteristic ingredients,such as, for example, oil of cloves (eugenol), mint oil (menthol) orthyme oil (thymol), also exhibit marked antimicrobial effectiveness.

The antibacterially effective substances are generally used inconcentrations of from about 0.1 to 0.3% by weight.

Suitable repellent active ingredients are compounds which are able todeter or repel certain animals, in particular insects, from people.These include, for example, 2-ethyl-1,3-hexanediol,N,N-diethyl-m-toluamide etc.

Suitable hyperemic substances, which stimulate blood flow in the skin,are, for example, essential oils, such as dwarf pine, lavender,rosemary, juniper berry, roast chestnut extract, birch leaf extract,marigold extract, ethyl acetate, camphor, menthol, peppermint oil,rosemary extract, eucalyptus oil, etc.

Suitable keratolytic and keratoplastic substances are, for example,salicylic acid, calcium thioglycolate, thioglycolic acid and its salts,sulfur, etc.

Suitable antidandruff active ingredients are, for example, sulfur,sulfur polyethylene glycol sorbitan monooleate, sulfur ricinolpolyethoxylate, zinc pyrithion, aluminum pyrithion, etc. Suitableantiphlogistics, which counteract skin irritations, are, for example,allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.

The cosmetic compositions according to the invention can comprise, ascosmetic and/or pharmaceutical active ingredient (and also ifappropriate as auxiliary), at least one cosmetically or pharmaceuticallyacceptable polymer.

Preference is given to compositions which additionally comprise at leastone nonionic, one anionic or one ampholytic polymer.

Anionic polymers preferred as additional polymers are, for example,homopolymers and copolymers of acrylic acid and methacrylic acid, andsalts thereof. These also include crosslinked polymers of acrylic acid,as available under the INCI name Carbomer. Such crosslinked homopolymersof acrylic acid are, for example, commercially available under the nameCarbopol® from BF GOODRICH. Preference is also given to hydrophobicallymodified crosslinked polyacrylate polymers, such as Carbopol®Ultrez 21from Noveon.

Further examples of suitable additional anionic polymers are copolymersof acrylic acid and acrylamide and salts thereof; sodium salts ofpolyhydroxycarboxylic acids, water-soluble or water-dispersiblepolyesters, polyurethanes and polyureas.

Preference is also given to compositions which additionally comprise apolyurethane as anionic polymer.

Particularly suitable additional polymers are the water-soluble orwater-dispersible polyurethanes described in DE 4225045 A1, which ishereby incorporated in its entirety by reference. Luviset®P.U.R. (BASF)is particularly suitable. Particular preference is also given tosilicone-containing polyurethanes, as are described in DE 19807908 A1,which is hereby incorporated in its entirety by reference.Luviset®Si-P.U.R. (BASF) is particularly suitable.

Particularly suitable polymers are copolymers of (meth)acrylic acid andpolyether acrylates, where the polyether chain is terminated with aC₈-C₃₀-alkyl radical. These include, for example, acrylate/beheneth-25methacrylate copolymers, which are available under the name Aculyn® fromRohm und Haas. Particularly suitable polymers are also copolymers oft-butyl acrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer®100P),copolymers of ethyl acrylate and methacrylic acid (e.g. Luviumer® MAE),copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid(Ultrahold®8, strong), copolymers of vinyl acetate, crotonic acid and ifappropriate further vinyl esters (e.g. Luviset® grades), maleicanhydride copolymers, if appropriate reacted with alcohol, anionicpolysiloxanes, e.g. carboxy functional ones, t-butyl acrylate,methacrylic acid (e.g. Luviskol®VBM), copolymers of acrylic acid andmethacrylic acid with hydrophobic monomers, such as, for example,C₄-C₃₀-alkyl esters of meth(acrylic acid), C₄-C₃₀-alkyl vinyl esters,C₄-C₃₀-alkyl vinyl ethers and hyaluronic acid. Examples of anionicpolymers are also vinyl acetate/crotonic acid copolymers, as arecommercially available, for example, under the names Resyn® (NationalStarch) and Gafset® (GAF) and vinylpyrrolidone/vinyl acrylatecopolymers, obtainable, for example, under the trade name Luviflex®(BASF). Further suitable polymers are the vinylpyrrolidone/acrylateterpolymer obtainable under the name Luviflex®VBM-35 (BASF) and sodiumsulfonate-containing polyamides or sodium sulfonate-containingpolyesters.

In addition, the group of suitable anionic polymers comprises, forexample, Balance® CR (National Starch; acrylate copolymer), Balance®0/55 (National Starch; acrylate copolymer), Balance® 47 (NationalStarch; octylacrylamide/acrylates/butylaminoethyl methacrylatescopolymer), Aquaflex® FX 64 (ISP;isobutylene/ethylmaleimide/hydroxyethylmaleimide copolymer), Aquaflex®SF-40 (ISP/National Starch; VP/vinyl caprolactam/DMAPA acrylatecopolymer), Allianz® LT-120 (ISP; Rohm & Haas; acrylate/C₁₋₂succinate/hydroxyacrylate copolymer), Aquarez® HS (Eastman;polyester-1), Diaformer® Z-400 (Clariant;methacryloylethylbetaine/methacrylate copolymer), Diaformer® Z-711(Clariant; methacryloylethyl N-oxide/methacrylate copolymer), Diaformer®Z-712 (Clariant; methacryloylethyl N-oxide/methacrylate copolymer),Omnirez® 2000 (ISP; monoethyl ester of poly(methyl vinyl ether/maleicacid in ethanol), Amphomer® HC (National Starch;acrylate/octylacrylamide copolymer), Amphomer® 28-4910 (National Starch;octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer),Advantage® HC 37 (ISP; terpolymer ofvinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylate),Advantage® LC55 and LC80 or LC A and LC E, Advantage® Plus (ISP;VA/butyl maleate/isobornyl acrylate copolymer), Aculyne® 258 (Rohm &Haas; acrylate/hydroxyl ester acrylate copolymer), Luviset® P.U.R.(BASF, polyurethane-1), Luviflex® Silk (BASF), Eastman® AQ 48 (Eastman),Styleze® CC-10 (ISP; VP/DMAPA acrylates copolymer), Styleze® 2000 (ISP;VP/acrylates/lauryl methacrylate copolymer), DynamX® (National Starch;polyurethane-14 AMP-acrylates copolymer), Resyn® XP (National Starch;acrylates/octylacrylamide copolymer), Fixomer® A-30 (Ondeo Nalco;polymethacrylic acid (and) acrylamidomethylpropanesulfonic acid),Fixate® G-100 (Noveon; AMP-acrylates/allyl methacrylate copolymer).

Suitable additional polymers are also the terpolymers ofvinylpyrrolidone, C₁-C₁₀-alkyl-cycloalkyl- and aryl (meth)acrylates andacrylic acid described in U.S. Pat. No. 3,405,084. Suitable additionalpolymers are also the terpolymers of vinylpyrrolidone, tert-butyl(meth)acrylate and (meth)acrylic acid described in EP-A-0 257 444 andEP-A-0 480 280. Suitable additional polymers are also the copolymersdescribed in DE-A-42 23 066 which comprise at least one (meth)acrylicester, (meth)acrylic acid and N-vinylpyrrolidone and/orN-vinylcaprolactam in copolymerized form. The disclosure of thesedocuments is hereby incorporated by reference.

Suitable polymers containing carboxylic acid groups are alsopolyurethanes containing carboxylic acid groups.

EP-A-636361 discloses suitable block copolymers with polysiloxane blocksand polyurethane/polyurea blocks which have carboxylic acid and/orsulfonic acid groups. Suitable silicone-containing polyurethanes arealso described in WO 97/25021 and EP-A-751 162. Suitable polyurethanesare also described in DE-A-42 25 045, which is hereby incorporated inits entirety by reference.

These polyurethanes are in principle constructed from

-   i) at least one compound which comprises two or more active hydrogen    atoms per molecule,-   ii) at least one carboxylic-acid-group-comprising diol or a salt    thereof and-   iii) at least one polyisocyanate.

Component i) is, for example, a diol, diamine, amino alcohol, or mixturethereof. The molecular weight of these compounds is preferably in arange from about 56 to 280. If desired, up to 3 mol % of said compoundscan be replaced by triols or triamines.

Diols i) which can be used are, for example, ethylene glycol, propyleneglycol, butylene glycol, neopentyl glycol, cyclohexanedimethylol, di-,tri-, tetra-, penta- or hexaethylene glycol and mixtures thereof.Preference is given to using neopentyl glycol and/orcyclohexanedimethylol. Suitable aminoalcohols i) are, for example,2-aminoethanol, 2-(N-methylamino)ethanol, 3-aminopropanol,4-aminobutanol, 1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol,4-methyl-4-aminopentan-2-ol etc. Suitable diamines i) are, for example,ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentaneand 1,6-diaminohexane, and α,ω-diaminopolyethers, which can be preparedby amination of polyalkylene oxides with ammonia.

Component i) may also be a polymer with a number-average molecularweight in the range from about 300 to 5000, preferably about 400 to4000, in particular 500 to 3000. Polymers i) which can be used are, forexample, polyesterdiols, polyetherols and mixtures thereof. Polyetherolsare preferably polyalkylene glycols, e.g. polyethylene glycols,polypropylene glycols, polytetrahydrofurans etc., block copolymers ofethylene oxide and propylene oxide or block copolymers of ethyleneoxide, propylene oxide and butylene oxide which comprise thecopolymerized alkylene oxide units in random distribution or in the formof blocks. Suitable polytetrahydrofurans i) can be prepared by cationicpolymerization of tetrahydrofuran in the presence of acidic catalysts,such as, for example, sulfuric acid or fluorosulfuric acid. Suchpreparation processes are known to the person skilled in the art.Polyesterdiols i) which can be used preferably have a number-averagemolecular weight in the range from about 400 to 5000, preferably 500 to3000, in particular 600 to 2000. Suitable polyesterdiols i) are allthose which are customarily used for preparing polyurethanes, inparticular those based on aromatic dicarboxylic acids, such asterephthalic acid, isophthalic acid, phthalic acid, Na or Ksulfoisophthalic acid etc., aliphatic dicarboxylic acids, such as adipicacid or succinic acid etc., and cycloaliphatic dicarboxylic acids, suchas 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid. Suitable diols are,in particular, aliphatic diols, such as ethylene glycol, propyleneglycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol,polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane,etc.

Suitable compounds II) which have two active hydrogen atoms and at leastone carboxylic acid group per molecule are, for example,dimethylolpropanoic acid and mixtures which comprise dimethylolpropanoicacid.

Component iii) is a customary aliphatic, cycloaliphatic and/or aromaticpolyisocyanate, such as tetramethylene diisocyanate, hexamethylenediisocyanate, methylene diphenyl diisocyanate, 2,4- and 2,6-tolylenediisocyanate and isomer mixtures thereof, o- and m-xylylenediisocyanate, 1,5-naphthylene diisocyanate, 1,4-cyclohexylenediisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof, inparticular isophorone diisocyanate and/or dicyclohexylmethanediisocyanate. If desired, up to 3 mol % of said compounds can bereplaced by triisocyanates.

Suitable additional polymers are also cationic polymers. These include,for example, polymers with the INCI name Polyquaternium, e.g. copolymersof vinylpyrrolidone/N-vinylimidazolium salts (Luviquat® FC, Luviquat®HM, Luviquat® MS, Luviquat® Care), copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Luviquat® PQ 11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat® Hold); cationic cellulose derivatives (polyquaternium-4 and-10), acrylamido copolymers (polyquaternium-7) and chitosan. Suitablecationic (quaternized) polymers are also Merquate® (polymer based ondimethyldiallylammonium chloride), Gafquat® (quaternary polymers whichare formed by reacting polyvinylpyrrolidone with quaternary ammoniumcompounds), Polymer® JR (hydroxyethylcellulose with cationic groups) andcationic vegetable-based polymers, e.g. guar polymers, such as theJaguar® grades from Rhodia.

Suitable additional polymers are also amphoteric or zwitterionicpolymers, such as the octylacrylamide/methylmethacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropylmethacrylate copolymers obtainable under the names Amphomer® (NationalStarch), and zwitterionic polymers which are disclosed, for example, inthe German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369and DE 37 08 451. Acrylamidopropyltrimethylammonium chloride/acrylicacid or methacrylic acid copolymers and alkali metal and ammonium saltsthereof are preferred zwitterionic polymers. Further suitablezwitterionic polymers are methacroylethylbetaine/methacrylatecopolymers, which are commercially available under the name Amersette®(AMERCHOL), and copolymers of hydroxyethyl methacrylate, methylmethacrylate, N,N-dimethylaminoethyl methacrylate and acrylic acid(Jordapon®).

Neutral polymers suitable as additional polymers are, for example,polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinylacetate and/or vinyl propionate, polysiloxanes, polyvinylcaprolactam andother copolymers with N-vinylpyrrolidone, polyethyleneimines and saltsthereof, polyvinylamines and salts thereof, cellulose derivatives,polyaspartic acid salts and derivatives. These include, for example,Luviflex® Swing (partially hydrolyzed copolymer of polyvinyl acetate andpolyethylene glycol, BASF).

Suitable polymers are also nonionic, water-soluble or water-dispersiblepolymers or oligomers, such as polyvinylcaprolactam, e.g. Luviskol® Plus(BASF), or polyvinylpyrrolidone and copolymers thereof, in particularwith vinyl esters, such as vinyl acetate, e.g. Luviskol® VA 37 (BASF);polyamides, e.g. based on itaconic acid and aliphatic diamines, as aredescribed, for example, in DE-A-43 33 238.

Suitable polymers are also nonionic, siloxane-containing, water-solubleor -dispersible polymers, e.g. polyethersiloxanes, such as Tegopren®(Goldschmidt) or Belsil® (Wacker).

The formulation base of pharmaceutical compositions according to theinvention preferably comprises pharmaceutically acceptable auxiliaries.Pharmaceutically acceptable auxiliaries are auxiliaries which are knownfor use in the field of pharmacy, food technology and related fields, inparticular those listed in the relevant pharmacopoeia (e.g. DAB Ph. Eur.BP NF), and other auxiliaries whose properties do not preclude aphysiological application.

Suitable auxiliaries may be: lubricants, wetting agents, emulsifying andsuspending agents, preservatives, antioxidants, antiirritatives,chelating agents, emulsion stabilizers, film formers, gel formers,odor-masking agents, resins, hydrocolloids, solvents, solubilitypromoters, neutralizing agents, permeation accelerators, pigments,quaternary ammonium compounds, regressing and supergreasing agents,ointment, cream or oil base substances, silicone derivatives,stabilizers, sterilants, propellants, drying agents, opacifiers,thickeners, waxes, plasticizers, white oils. One embodiment in thisrespect is based on specialist knowledge, as represented, for example,in Fiedler, H. P. Lexikon der Hilfsstoffe für Pharmazie, Kosmetik undangrenzende Gebiete [Lexikon of auxiliaries for pharmacy, cosmetics andrelated fields], 4^(th) edition, Aulendorf: ECV Editio-Kantor-Verlag,1996.

To prepare the dermatological compositions according to the invention,the active ingredients can be mixed or diluted with a suitable auxiliary(excipient). Excipients may be solid, semisolid or liquid materialswhich can serve as a vehicle, carrier or medium for the activeingredient. The admixing of further auxiliaries takes place, if desired,in the manner known to the person skilled in the art. In addition, thepolymers and polyelectrolyte complexes are suitable as auxiliaries inpharmacy, preferably as or in (a) coating(s) or binder(s) for solid drugforms. They can also be used in creams and as tablet coatings and tabletbinders.

Pharmaceutical Preparations

One subject-matter of the invention relates to pharmaceuticalcompositions comprising the polymers according to the invention andpharmaceutically customary active ingredients and additives.

Solid pharmaceutical administration forms, such as tablets, capsules,pellets, granules, crystals etc., are coated, i.e. provided with a filmcovering, for very different reasons.

Thus, for example, a bad odor or taste can be masked, and theswallowability can be improved. The stability of the active ingredientcan be increased as a result of the coating since less water vapor andoxygen passes to the inside of the tablet. The administration forms lookbetter and can be better differentiated by incorporating dyes. Moreover,the release rate of the active ingredient can be adjusted in particularby virtue of the film coating.

In general, a distinction is made between instant release forms andslow-release forms.

In the case of instant release forms, the disintegration of the tabletand the release of the active ingredient from the administration formshould if possible not be influenced by the coating, and for this reasonthe film coating must dissolve rapidly in the gastric juice. Inaddition, it must have good film properties. The tensile strength andthe elongation at break should be high so that the film coatingwithstands mechanical effects as arise during pharmaceuticalprocessing—in particular formulation—and also during dispatch and/orstorage.

One product which is frequently used for coating instant release tabletsis hydroxypropylmethylcellulose (HPMC). Hydroxypropylmethylcellulose hasa sharp viscosity increase in aqueous solution as the concentrationincreases. Similar behavior is also demonstrated byhydroxypropylcellulose (HPC).

Since the film-former solution for the coating of tablets has to befinely atomized and the formed droplets must thoroughly wet the surfaceof the tablets and must also be readily sprayable, the viscosity shouldnot exceed a certain limit (between 150 and 250 mPas), which isdependent on the type of spray nozzle and the instrument. For thisreason, in the case of HPMC, only relatively low film-formerconcentrations can be used.

The recommended concentration of Pharmacoat® 606 (Shin-etsu) stated inthe literature is 5 to 7% by weight (Pharmaceutical Coating Technology,Ed. Graham Cole, Taylor and Francis Ltd. 1995 and technical datasheetsfrom the manufacturer). These low spray concentrations lead torelatively long processing times and thus high costs.

Moreover, hydroxypropylmethylcellulose has further disadvantages, interalia, with regard to wetting behavior, pigment-binding capacity,mechanical properties of the films, hygroscopicity, and permeability towater vapor and oxygen, dissolution rate and disintegration timedifference between film tablets and core.

The low elasticity of the films made of hydroxypropylmethylcelluloseoften leads to the film tablets rupturing when stored in damp conditionsas a result of the core swelling. Even the use of plasticizers does notresult in noteworthy improvements of this problem. Instead, it can leadto sticky films and, as a result of migration, to changes in theproperties of the tablets.

Oral drug forms with a release of medicament over a prolonged periodwith the aim of prolonging the effect of the active component (generallyslow-release forms) are increasingly gaining importance. They areadvantageously associated with improved patient compliance as a resultof reduced taking frequency, a reduction in side effects throughavoiding plasma peaks, more uniform level of the medicament in theblood, and the avoidance of local irritations. Besides the formulationof medicament-containing cores which have been coated with awater-insoluble but semipermeable or pore-containing film through whichthe medicament diffuses, the release can be controlled and prolonged byembedding the medicament into matrices. In addition, the use of ionexchanger resins and therapeutic systems (e.g. OROS) is possible.

The embedding of the medicament into hydrocolloid matrices in particularoffers the advantages of simple and cost-effective preparation and highmedicament safety since dose dumping effects cannot arise. Theauxiliaries generally used here, such as hydroxypropylmethylcellulose(HPMC), hydroxypropylcellulose, alginic acid or alginates, and xanthan,have application disadvantages. These are: inadequate flow properties,which hinder direct tableting, dependency of the medicament release onthe osmolarity (salt content) and on the pH of the release medium. Thisis true for HPMC as well as for hydroxypropylcellulose, xanthan andalginates. The use of xanthan also leads to tablets of lower hardness,the direct tableting of alginates results in compacts with only slightslow-release properties (max. 8 h). The natural swelling materials (e.g.alginates) have a high charge variability overall.

Binders are used in pharmaceutical administration forms in order toincrease the processability and the mechanical strength. They areusually used in tablets, granules and pellets and lead to improvedflowability, higher fracture resistance and lower friability.

The binders currently used, such as maltodextrin orpolyvinylpyrrolidones, often lead to unsatisfactory fracture resistancesand friabilities. Other binders, such as starch pastes andhydroxypropylmethylcellulose (HPMC) can only be used in lowconcentrations on account of their high viscosity.

In addition, film-forming auxiliaries are used in solutions and sprayswhich are applied to the skin or mucosa or else introduced systemicallyto the body. Examples thereof are preparations for the treatment ofwounds, spray dressings, but also preparations for application to intactskin or mucosa. Here, the skin is protected by a film and the activeingredients can penetrate into and/or through the skin.

In the case of transdermal therapeutic systems and in the case of woundplasters, as is the case with the abovementioned administration forms,adequate flexibility is required which currently available products donot have. The use of possible plasticizers for achieving the necessaryflexibility is undesired for toxicological and pharmacological reasons.

An object of the present invention was to provide water-soluble orwater-dispersible polymers as coatings, binders and/or film formers inpharmaceutical preparations which do not have the disadvantages givenabove.

Surprisingly, it has been found that the polymers according to theinvention are suitable for use in pharmaceutical preparations.

They are particularly suitable as coatings, binders, film formers andalso as active ingredient release matrix in pharmaceutical preparations.

The polymers according to the invention can be used in a large number ofpharmaceutical preparations.

Examples of coated preparations which may be mentioned are film tablets,film microtablets, sugar-coated tablets, coated pastilles, capsules,crystals, granules or pellets.

Binder-containing preparations are, for example, tablets, microtablets,cores, granules or pellets.

In addition, the polymers according to the invention can be used for thepreparation of solutions and sprays which, applied to skin or mucosa,form a film.

Examples thereof are spray dressings for wounds, disinfection sprays,solutions with mycostatics, mouth sprays or solutions containingantibiotics etc. Use in transdermal therapeutic systems is alsopossible.

The polymers according to the invention readily wet lipophilic surfacesand have excellent protective colloid properties. When incorporated intosuspensions and emulsions, they deposit themselves on the particles ofthe disperse phase and stabilize these. They can therefore be used aswetting auxiliaries and stabilizers in disperse systems.

As a result of interaction with sparingly water-soluble medicaments,they improve their solubility and dissolution rate, as a result of whichresorbability and bioavailability of the medicaments are improved. Thisadvantageous effect is evident, for example, with administration formsin which the active ingredient is not present in dissolved form, suchas, for example, tablets, granules, suspensions etc.

The polymers according to the invention can, if appropriate, also incombination with other auxiliaries be processed together with activeingredients to give polymer-active ingredient melts which are eitherextruded and calendered to give medicaments or, following extrusion, arecomminuted to give granules or powders and only then processed into drugforms, for example compressed to give tablets. Here, the polymersaccording to the invention introduce the properties already listed aboveinto the preparations.

In different pharmaceutical preparations, the polymers according to theinvention can fulfil the following functions in excellent manner:

dispersion auxiliary, suspension auxiliary, wetting agent, solubilizerfor sparingly soluble medicaments, emulsifier, crystallizationinhibitor, anticaking active ingredient, protective colloid, bioadhesivefor prolonging and intensifying contact with the mucosa, spreadingauxiliary, viscosity regulator, auxiliary for preparing solid solutionswith medicaments, auxiliary for adjusting the active ingredient releasein slow-release formulations.

The solubility of the polymers according to the invention can beadjusted within certain limits through suitable choice of the degree ofneutralization.

Thus, polymers according to the invention which are insoluble or onlyslightly soluble, but dispersible in water can also be used asslow-release polymers.

When used for producing suppositories and vaginal globuli, the polymersaccording to the invention ensure on the one hand the flexibility of theadministration form and, on the other hand, promote disintegration andthe dissolution of active ingredient and they coat the mucosa with anactive-ingredient-containing film which enhances absorption.

Tablets swell to varying degrees depending on the auxiliaries and activeingredients used, the storage time and the storage conditions, such astemperature and humidity. A rigid film coating suffers cracks if thecore swells. The elasticity of film formers is therefore an importantparameter.

The polymers according to the invention, if appropriate neutralized, canbe applied in pure form or else together with the customary auxiliariesto the active-ingredient-containing core. Customary auxiliaries are, forexample, color pigments for coloring, white pigments, such as titaniumdioxide, for increasing coverage, talc and silicon dioxide asdetackifiers, polyethylene glycols, glycerol, propylene glycol,triacetin, triethyl citrate as plasticizer and various surface-activesubstances, such as sodium lauryl sulfate, polysorbate 80, pluronics andcremophors, for improving the wetting behavior. The substances specifiedby way of example do not represent any limitation. All known additivessuitable for film coatings that are soluble in gastric juice can beused.

Coating methods which may be used are the customary methods, such ascoating in a fluidized bed or a horizontal drum coater, and dip-coatingand pan-coating methods. Besides the tablet application, the polymersaccording to the invention can also be used for coating otherpharmaceutical preparations, such as granules, pellets, crystals orcapsules. The novel coatings are applied in a conventional thickness offrom 5 to 200 μm, preferably 10 to 100 μm.

When used as binders, a distinction is made between wet and dry bindersdepending on the processing method. The latter are used inter alia indirect tableting and in dry granulation or compaction. In these cases,the binder is mixed with the active ingredient and, if appropriate,further auxiliaries and then subjected to direct tableting, orgranulation or compaction.

In contrast to this, for wet granulation, the activeingredient-auxiliary mixture is moistened with a solution of the binderin water or an organic solvent, and the moist mass is forced through ascreen and then dried. The moistening and drying can also take place inparallel, as, for example, in fluidized-bed granulation.

For optimal processing, the binder should give low-viscosity solutionssince viscous solutions lead to inhomogenous granules.

A binder should result in uniform, hard, abrasion-resistant granules ortablets. Fracture resistance is particularly important in particular fortablets because many active ingredients are difficult to compress andthus afford tablets with inadequate mechanical stability.

In addition, the disintegration of the drug forms, and the rate ofrelease of the active ingredients should experience negligible adverseeffects from the binder.

Examples of the most commonly used binders are polyvinylpyrrolidone,vinyl acetate/vinylpyrrolidone copolymers, gelatin, starch paste,maltodextrins, hydroxyalkylated and carboxyalkylated cellulosederivatives, such as hydroxypropylmethylcellulose, methylcellulose,sodiumcarboxymethylcellulose and types of natural gums, such as gumArabic, pectin or alginate.

Many of these binders have a high viscosity in solution and aredifficult to process. The high viscosity means that the powderedparticles to be granulated are wetted poorly and unevenly, resulting ininadequate granule strength and an unfavorable particle sizedistribution.

Many binders are, moreover, hygroscopic and swell when water isabsorbed. This may result in dramatic changes in the properties ofgranules and tablets.

Surprisingly, it has now been found that the sulfonated polymerscomprising sulfone groups have excellent binding effects and, moreover,have a negligible effect on disintegration at concentrations in therange from 0.5 to 20% by weight, preferably 1 to 10% by weight, of thetotal amount of the formulation. On account of the good wettingcharacteristics, it is moreover possible for the release of activeingredients with poor solubility to be improved. The comparatively lowviscosity of the polymer solutions should also be emphasized.

If required, the pharmaceutically acceptable additives and auxiliariessuitable for skin cosmetic and/or hair cosmetic preparations can ofcourse be used in the pharmaceutical preparations.

When the polymers are used as binders, granules and tablets are obtainedwhich have exceptional mechanical stability and are stable even overlong storage periods.

A further preferred embodiment of the invention is skin-cleansingcompositions.

Preferred skin-cleansing compositions are soaps of liquid to gelconsistency, such as transparent soaps, luxury soaps, deodorant soaps,cream soaps, baby soaps, skin protection soaps, abrasive soaps andsyndets, pasty soaps, lubricating soaps and washing pastes, liquidwashing, showering and bathing preparations, such as washing lotions,shower baths and gels, foam baths, oil baths and scrub preparations,shaving foams, lotions and creams.

A further preferred embodiment of the invention is cosmetic compositionsfor the care and protection of the skin, nail care compositions orpreparations for decorative cosmetics.

Suitable skin cosmetic compositions are, for example, face tonics, facemasks, deodorants and other cosmetic lotions. Compositions for use indecorative cosmetics comprise, for example, concealing sticks, stagemake-up, mascara and eyeshadows, lipsticks, kohl pencils, eyeliners,blushers, powders and eyebrow pencils.

In addition, the copolymers according to the invention can be used innose strips for pore cleansing, in antiacne compositions, repellents,shaving compositions, hair-removal compositions, intimate carecompositions, footcare compositions and in babycare.

The skin-care compositions according to the invention are, inparticular, W/O or O/W skin creams, day and night creams, eye creams,face creams, antiwrinkle creams, moisturizing creams, bleaching creams,vitamin creams, skin lotions, care lotions and moisturizing lotions.

Skin cosmetic and dermatological compositions based on the copolymersaccording to the invention exhibit advantageous effects. The polymerscan, inter alia, contribute to the moisturization and conditioning ofthe skin and to the improvement in the feel of the skin. The polymerscan also act as thickeners in the formulations. The addition of thepolymers according to the invention can achieve a considerableimprovement in the skin compatibility in certain formulations.

Skin cosmetic and dermatological compositions preferably comprise atleast one copolymer according to the invention in an amount of fromabout 0.001 to 30% by weight, preferably 0.01 to 20% by weight, veryparticularly preferably 0.1 to 12% by weight, based on the total weightof the composition.

Particularly photoprotective compositions based on the copolymersaccording to the invention have the property of increasing the residencetime of the UV-absorbing ingredients compared with customary auxiliariessuch as polyvinylpyrrolidone.

Depending on the field of use, the compositions according to theinvention can be applied in a form suitable for skincare, such as, forexample, in the form of a cream, foam, gel, stick, mousse, milk, spray(pump spray or propellant-containing spray) or lotion.

Besides the copolymers according to the invention and suitable carriers,the skin cosmetic preparations can also comprise further activeingredients and auxiliaries customary in skin cosmetics, as describedabove. These include, preferably, emulsifiers, preservatives, perfumeoils, cosmetic active ingredients, such as phytantriol, vitamin A, E andC, retinol, bisabolol, panthenol, photoprotective agents, bleaches,colorants, tinting agents, tanning agents, collagen, proteinhydrolyzates, stabilizers, pH regulators, dyes, salts, thickeners, gelformers, bodying agents, silicones, humectants, regreasing agents andfurther customary additives.

Preferred oil and fat components of the skin cosmetic and dermatologicalcompositions are the abovementioned mineral and synthetic oils, such as,for example, paraffins, silicone oils and aliphatic hydrocarbons withmore than 8 carbon atoms, animal and vegetable oils, such as, forexample, sunflower oil, coconut oil, avocado oil, olive oil, lanolin, orwaxes, fatty acids, fatty acid esters, such as, for example,triglycerides of C₆-C₃₀-fatty acids, wax esters, such as, for example,jojoba oil, fatty alcohols, vaseline, hydrogenated lanolin andacetylated lanolin, and mixtures thereof.

The copolymers according to the invention can also be mixed withconventional polymers if specific properties are to be set.

To set certain properties, such as, for example, improvement in the feelto the touch, the spreading behavior, the water resistance and/or thebinding of active ingredients and auxiliaries, such as pigments, theskin cosmetic and dermatological preparations can additionally alsocomprise conditioning substances based on silicone compounds. Suitablesilicone compounds are, for example, polyalkylsiloxanes,polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes orsilicone resins.

The cosmetic or dermatological preparations are prepared by customarymethods known to the person skilled in the art.

Preferably, the cosmetic and dermatological compositions are in the formof emulsions, in particular in the form of water-in-oil (W/O) oroil-in-water (O/W) emulsions. It is, however, also possible to chooseother types of formulations, for example hydrodispersions, gels, oils,oleogels, multiple emulsions, for example in the form of W/O/W, or O/W/Oemulsions, anhydrous ointments and ointment bases, etc.

Emulsions are prepared by known methods. Besides at least one copolymeraccording to the invention, the emulsions generally comprise customaryconstituents, such as fatty alcohols, fatty acid esters and, inparticular, fatty acid triglycerides, fatty acids, lanolin andderivatives thereof, natural or synthetic oils or waxes and emulsifiersin the presence of water. The selection of the additives specific to thetype of emulsion and the preparation of suitable emulsions is described,for example, in Schrader, Grundlagen und Rezepturen der Kosmetika[Fundamentals and formulations of cosmetics], Hüthig Buch Verlag,Heidelberg, 2^(nd) edition, 1989, third part, which is herebyincorporated by reference.

A suitable emulsion, e.g. for a skin cream etc., generally comprises anaqueous phase which is emulsified by means of a suitable emulsifiersystem in an oil or fat phase. To prepare the aqueous phase, a copolymeraccording to the invention can be used.

Preferred fat components which can be present in the fat phase of theemulsions are: hydrocarbon oils, such as paraffin oil, purcellin oil,perhydrosqualene and solutions of microcrystalline waxes in these oils;animal or vegetable oils, such as sweet almond oil, avocado oil,calophylum oil, lanolin and derivatives thereof, castor oil, sesame oil,olive oil, jojoba oil, karite oil, hoplostethus oil; mineral oils whosedistillation start-point under atmospheric pressure is about 250° C. andwhose distillation end-point is at 410° C., such as, for example,vaseline oil; esters of saturated or unsaturated fatty acids, such asalkyl myristates, e.g. isopropyl, butyl or cetyl myristate, hexadecylstearate, ethyl or isopropyl palmitate, octanoic or decanoic acidtriglycerides and cetyl ricinoleate.

The fatty phase can also comprise silicone oils soluble in other oils,such as dimethylpolysiloxane, methylphenylpolysiloxane and the siliconeglycol copolymer, fatty acids and fatty alcohols.

Besides the copolymers according to the invention, waxes can also beused, such as, for example, carnauba wax, candililla wax, beeswax,microcrystalline wax, ozocerite wax and Ca, Mg and Al oleates,myristates, linoleates and stearates.

In addition, an emulsion according to the invention can be in the formof an O/W, emulsion. Such an emulsion usually comprises an oil phase,emulsifiers which stabilize the oil phase in the water phase, and anaqueous phase which is usually in thickened form. Suitable emulsifiersare preferably O/W emulsifiers, such as polyglycerol esters, sorbitanesters or partially esterified glycerides.

According to a further preferred embodiment, the compositions accordingto the invention are a shower gel, a shampoo formulation or a bathpreparation.

Such formulations comprise at least one copolymer according to theinvention and usually anionic surfactants as base surfactants andamphoteric and/or nonionic surfactants as cosurfactants. Furthersuitable active ingredients and/or auxiliaries are generally chosen fromlipids, perfume oils, dyes, organic acids, preservatives andantioxidants, and thickeners/gel formers, skin conditioners andhumectants.

These formulations preferably comprise 2 to 50% by weight, preferably 5to 40% by weight, particularly preferably 8 to 30% by weight ofsurfactants, based on the total weight of the formulation.

In the washing, showering and bathing preparations, all of the anionic,neutral, amphoteric or cationic surfactants customary in body-cleansingcompositions can be used.

Suitable anionic surfactants are, for example, alkyl sulfates, alkylether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates,alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acylisothionates, alkyl phosphates, alkyl ether phosphates, alkyl ethercarboxylates, alpha-olefin sulfonates, in particular the alkali metaland alkaline earth metal salts, e.g. sodium, potassium, magnesium,calcium, and ammonium and triethanolamine salts. The alkyl ethersulfates, alkyl ether phosphates and alkyl ether carboxylates can havebetween 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to3 ethylene oxide units, in the molecule.

These include, for example, sodium lauryl sulfate, ammonium laurylsulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate,sodium lauryl sarcosinate, sodium oleyl succinate, ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolaminedodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines,alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkylcarboxyglycinates, alkyl amphoacetates or propionates, alkylamphodiacetates or dipropionates.

For example, cocodimethylsulfopropylbetaine, laurylbetaine,cocamidopropylbetaine or sodium cocamphopropionate can be used.

Suitable nonionic surfactants are, for example, the reaction products ofaliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in thealkyl chain, which may be linear or branched, with ethylene oxide and/orpropylene oxide. The amount of alkylene oxide is about 6 to 60 mols permole of alcohol. Also suitable are alkylamine oxides, mono- ordialkylalkanolamides, fatty acid esters of polyethylene glycols,ethoxylated fatty acid amides, alkyl polyglycosides or sorbitan etheresters.

In addition, the washing, showering and bathing preparations cancomprise customary cationic surfactants, such as, for example,quaternary ammonium compounds, for example cetyltrimethylammoniumchloride.

In addition, the shower gel/shampoo formulations can comprisethickeners, such as, for example, sodium chloride, PEG-55, propyleneglycol oleate, PEG-120 methylglucose dioleate and others, andpreservatives, further active ingredients and auxiliaries and water.

A particularly preferred embodiment of the invention is hair-treatmentcompositions.

Hair-treatment compositions according to the invention preferablycomprise at least one copolymer according to the invention in an amountin the range from about 0.1 to 30% by weight, preferably 0.5 to 20% byweight, based on the total weight of the composition.

The hair-treatment compositions according to the invention arepreferably in the form of a setting foam, hair mousse, hair gel,shampoo, hairspray, hair foam, end fluids, neutralizers for permanentwaves, hair colorants and bleaches or “hot-oil treatments”. Depending onthe field of application, the hair cosmetic preparations can be appliedin the form of an (aerosol) spray, (aerosol) foam, gel, gel spray,cream, lotion or wax. Hairsprays here comprise both aerosol sprays andalso pump sprays without propellant gas. Hair foams comprise bothaerosol foams and also pump foams without propellant gas. Hairsprays andhair foams preferably comprise predominantly or exclusivelywater-soluble or water-dispersible components. If the compounds used inthe hairsprays and hair foams according to the invention arewater-dispersible, they can be applied in the form of aqueousmicrodispersions with particle diameters of from usually 1 to 350 nm,preferably 1 to 250 nm. The solids contents of these preparations arehere usually in a range from about 0.5 to 20% by weight. Thesemicrodispersions generally require no emulsifiers or surfactants fortheir stabilization.

In a preferred embodiment of the invention, the compositions accordingto the invention comprise a fraction of volatile organic components(VOC) of at most 80% by weight, particularly preferably at most 55% byweight.

The hair cosmetic formulations according to the invention comprise, in apreferred embodiment,

-   a) 0.05 to 20% by weight of at least one copolymer according to the    invention,-   b) 20 to 99.95% by weight of water and/or alcohol,-   c) 0 to 50% by weight of at least one propellant gas,-   d) 0 to 5% by weight of at least one emulsifier,-   e) 0 to 3% by weight of at least one thickener, and-   f) up to 25% by weight of further constituents.

Alcohol is understood as meaning all alcohols customary in cosmetics,e.g. ethanol, isopropanol, n-propanol.

Further constituents are understood as meaning the additives customaryin cosmetics, for example propellants, antifoams, interface-activecompounds, i.e. surfactants, emulsifiers, foam formers and solubilizers.The interface-active compounds used may be anionic, cationic, amphotericor neutral. Further customary constituents may also be, for example,preservatives, perfume oils, opacifiers, active ingredients, UV filters,care substances, such as panthenol, collagen, vitamins, proteinhydrolyzates, alpha- and beta-hydroxycarboxylic acids, proteinhydrolyzates, stabilizers, pH regulators, dyes, viscosity regulators,gel formers, dyes, salts, humectants, regreasing agents, complexingagents and further customary additives.

All ingredients suitable for cosmetic compositions may, if appropriate,also be used for the hair cosmetic compositions.

These also include all styling and conditioning polymers known incosmetics which can be used in combination with the polymers accordingto the invention if very specific properties are to be set.

To set certain properties, the preparations can additionally alsocomprise conditioning substances based on silicone compounds. Suitablesilicone compounds are, for example, polyalkylsiloxanes,polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, siliconeresins or dimethicone copolyols (CTFA) and amino-functional siliconecompounds such as amodimethicones (CTFA).

The copolymers according to the invention are particularly suitable assetting agents in hairstyling preparations, in particular hairsprays(aerosol sprays and pump sprays without propellant gas) and hair foams(aerosol foams and pump foams without propellant gas).

In a preferred embodiment, spray preparations comprise

-   a) 0.1 to 10% by weight of at least one copolymer according to the    invention,-   b) 20 to 99.9% by weight of water and/or alcohol,-   c) 0 to 70% by weight of at least one propellant,-   d) 0 to 20% by weight of further constituents.

Propellants are the propellants customarily used for hairsprays andaerosol foams. Preference is given to mixtures of propane/butane,pentane, dimethyl ether, 1,1-difluoroethane (HFC-152a), carbon dioxide,nitrogen or compressed air.

A formulation for aerosol hair foams preferred according to theinvention comprises

-   a) 0.1 to 10% by weight of at least one copolymer according to the    invention,-   b) 55 to 99.8% by weight of water and/or alcohol,-   c) 5 to 20% by weight of a propellant,-   d) 0.1 to 5% by weight of an emulsifier,-   e) 0 to 10% by weight of further constituents.

Emulsifiers which can be used are all of the emulsifiers customarilyused in hair foams. Suitable emulsifiers may be nonionic, cationic oranionic or amphoteric.

Propellants which are particularly suitable for aerosol foams aremixtures of dimethyl ether and, if appropriate halogenated,hydrocarbons, such as propane, butane, pentane or HFC-152 a.

Examples of nonionic emulsifiers (INCI nomenclature) are laureths, e.g.laureth-4; ceteths, e.g. cetheth-1, polyethylene glycol cetyl ether;ceteareths, e.g. cetheareth-25, polyglycol fatty acid glycerides,hydroxylated lecithin, lactyl esters of fatty acids, alkylpolyglycosides.

Examples of cationic emulsifiers arecetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate, cetyltrimoniumchloride, cetyltrimmonium bromide, cocotrimonium methyl sulfate,quaternium-1 to x (INCI).

Anionic emulsifiers can, for example, be chosen from the group of alkylsulfates, alkyl ether sulfates, alkylsulfonates, alkylarylsulfonates,alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyltaurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates,alkyl ether carboxylates, alpha-olefinsulfonates, in particular thealkali metal and alkaline earth metal salts, e.g. sodium, potassium,magnesium, calcium, and ammonium and triethanolamine salts. The alkylether sulfates, alkyl ether phosphates and alkyl ether carboxylates canhave between 1 and 10 ethylene oxide or propylene oxide units,preferably 1 and 3 ethylene oxide units, in the molecule.

A preparation suitable according to the invention for styling gels can,for example, have the following composition:

-   a) 0.1 to 10% by weight of at least one copolymer according to the    invention,-   b) 80 to 99.85% by weight of water and/or alcohol,-   c) 0 to 3% by weight, preferably 0.05 to 2% by weight, of a gel    former,-   d) 0 to 20% by weight of further constituents.

The use of gel formers may, however, be advantageous for establishingspecific rheological or other application properties of the gels. Gelformers which can be used are all gel formers customary in cosmetics.These include slightly crosslinked polyacrylic acid, for exampleCarbomer (INCI), cellulose derivatives, e.g. hydroxypropylcellulose,hydroxyethylcellulose, cationically modified celluloses,polysaccharides, e.g. xanthan gum, caprylic/capric triglyceride, sodiumacrylate copolymers, Polyquaternium-32 (and) paraffinum liquidum (INCI),sodium acrylate copolymers (and) paraffinum liquidum (and) PPG-1trideceth-6, acrylamidopropyltrimonium chloride/acrylamide copolymers,steareth-10 alkyl ether acrylate copolymers, polyquaternium-37 (and)paraffinum liquidum (and) PPG-1 trideceth-6, polyquaternium 37 (and)propylene glycol dicaprate dicaprylate (and) PPG-1 trideceth-6,polyquaternium-7, polyquaternium-44.

The copolymers according to the invention can be used in cosmeticpreparations as conditioners.

The copolymers according to the invention, as defined above, canpreferably be used in shampoo formulations as setting and/orconditioning agents. Preferred shampoo formulations comprise

-   a) 0.05 to 10% by weight of at least one copolymer according to the    invention,-   b) 25 to 94.95% by weight of water,-   c) 5 to 50% by weight of surfactants,-   c) 0 to 5% by weight of a further conditioner,-   d) 0 to 10% by weight of further cosmetic constituents.

In the shampoo formulations, all of the anionic, neutral, amphoteric orcationic surfactants used customarily in shampoos can be used.

Suitable anionic surfactants are, for example, alkyl sulfates, alkylether sulfates, alkylsulfonates, alkylarylsulfonates, alkyl succinates,alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acylisothionates, alkyl phosphates, alkyl ether phosphates, alkyl ethercarboxylates, alpha-olefinsulfonates, in particular the alkali metal andalkaline earth metal salts, e.g. sodium, potassium, magnesium, calcium,and ammonium and triethanolamine salts. The alkyl ether sulfates, alkylether phosphates and alkyl ether carboxylates can have between 1 and 10ethylene oxide or propylene oxide units, preferably 1 and 3 ethyleneoxide units, in the molecule.

Examples of suitable compounds are sodium lauryl sulfate, ammoniumlauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ethersulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammoniumlauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolaminedodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines,alkylamidopropylbetaines, alkylsulfobetaines, alkyl glycinates, alkylcarboxyglycinates, alkyl amphoacetates or amphopropionates,alkylamphodiacetates or amphodipropionates.

For example, cocodimethylsulfopropylbetaine, laurylbetaine,cocamidopropylbetaine or sodium cocamphopropionate can be used.

Suitable nonionic surfactants are, for example, the reaction products ofaliphatic alcohols or alkylphenols having 6 to 20 carbon atoms in thealkyl chain, which may be linear or branched, with ethylene oxide and/orpropylene oxide. The amount of alkylene oxide is about 6 to 60 mols permole of alcohol. In addition, alkylamine oxides, mono- ordialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters are suitable.

Furthermore, the shampoo formulations can comprise customary cationicsurfactants, such as, for example, quaternary ammonium compounds, forexample cetyltrimethylammonium chloride.

In the shampoo formulations, conditioners customary for achievingcertain effects can be used in combination with the copolymers accordingto the invention. These include, for example, the abovementionedcationic polymers with the INCI name Polyquaternium, in particularcopolymers of vinylpyrrolidone/N-vinylimidazolium salts (Luviquat® FC,Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers ofN-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized withdiethyl sulfate (Luviquat® PQ 11), copolymers ofN-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts(Luviquat® Hold); cationic cellulose derivatives (polyquaternium-4 and-10), acrylamide copolymers (polyquaternium-7). It is also possible touse protein hydrolyzates, and conditioning substances based on siliconecompounds, for example polyalkylsiloxanes, polyarylsiloxanes,polyarylalkylsiloxanes, polyethersiloxanes or silicone resins. Furthersuitable silicone compounds are dimethicone copolyols (CTFA) andamino-functional silicone compounds, such as amodimethicones (CTFA).Cationic guar derivatives such as guarhydroxypropyltrimonium chloride(INCI) can also be used.

The invention further provides the use of a copolymer, as defined above,as auxiliary in pharmacy, preferably as or in (a) coating(s) for soliddrug forms, for modifying rheological properties, as surface-activecompound, as or in (an) adhesive(s), and as or in (a) coating(s) for thetextile, paper, printing and leather industry.

The invention is explained in more detail with reference to thefollowing nonlimiting examples.

Preparation of the Copolymers:

Preparation Procedure for Copolymers which Comprise no N-vinyllactam(Method A): Example No. 10   500 g of 30% strength by weightethanol-water [2:1] solution of P(EMA/MAA/AA/NtBAEMA) 72:22:3:3 Initialcharge   102 g water   63 g ethanol  13.1 g feed 1  0.81 g feed 2 Feed1: 108.0 g ethyl methacrylate  33.0 g methacrylic acid  4.5 g acrylicacid  4.5 g N-tert-butylaminoethyl methacrylate 112.0 g ethanol Feed 2 2.25 g Waco V50   14 g water Feed 3  0.75 tert-butyl perpivalate 75%strength 29.75 g ethanol Feed 4  39.7 g aminomethylpropanol AMP 26.48water   96 g ethanol

In a stirred apparatus with reflux condenser, internal thermometer andfour separate feed devices, 13.1 g of feed 1, 0.81 of feed 2, 102.0 g ofwater and 63 g of ethanol were initially introduced and the mixture washeated to about 75° C. with stirring.

After the onset of polymerization, evident from a slight increase inviscosity, the remainder of feed 1 was added over the course of threehours and the remainder of feed 2 was added over the course of fourhours at 75° C. The reaction solution was after-stirred for about afurther two hours at 75° C. Feed 3 was metered in at about 75° C. over30 minutes. The polymer mixture was after-polymerized for about afurther two hours at 80° C. The polymer solution was neutralized withAMP in feed 4 over 10 minutes. This gave 500 g of a 30% aqueousethanolic polymer solution.

Products 1-13 (Tab.1) were synthesized in accordance with thisprocedure.

Preparation Procedure for Copolymers which Comprise N-Vinyllactam(Method B): Example No. 19   500 g of 30% strength ethanol-water [30:40]solution of P(EMA/VP/MAA/VI) 50:30:15:5 Initial charge  64.0 g water  174 g ethanol  8.12 g feed 1  2.78 g feed 2 Feed 1:   75 g ethylmethacrylate  45.0 g vinylpyrrolidone  22.5 g methacrylic acid  7.5 gvinylimidazole 12.42 N,N-dimethylethanolamine Feed 2  3.0 g Waco ®V50 52.5 g water Feed 3  0.75 tert-butyl perpivalate 75% strength 29.75 gethanol

In a stirred apparatus with reflux condenser, internal thermometer andfour separate feed devices, 8.12 g of feed 1, 2.78 g of feed 2, 64 g ofwater and 174 g of ethanol were initially introduced and the mixture washeated to about 65° C. with stirring.

After the onset of polymerization, evident from a slight increase inviscosity, the remainder of feed 1 was added over the course of threehours and the remainder of feed 2 was added over the course of fourhours at 67° C. The reaction solution was after-stirred for about afurther two hours at 70° C.

Feed 3 was metered in at about 70° C. over 30 minutes. The polymermixture was after-polymerized for about a further two hours at 80° C.Then, at an external temperature Te of 120° C., the reaction mixture wassteam-distilled until an internal temperature Ti of about 100° C. wasreached. The polymer solution was further treated with steam for 1 hourat 10° C., then adjusted to pH 8-8.4 with aminomethylpropanol. Theviscous, cloudy polymer solution was stabilized with 150 g of ethanoland diluted with water to a solids content of 30%. This gave 500 g of a30% slightly cloudy, stable polymer solution.

Products 14-22 (Tab.2) were synthesized in accordance with thisprocedure.

Abbreviations used:

-   MAA methacrylic acid-   AA acrylic acid-   VCap vinylcaprolactam-   VP N-vinylpyrrolidone-   MMA methyl methacrylate-   EMA ethyl methacrylate-   n-BMA n-butyl methacrylate-   t-BMA t-butyl methacrylate-   t-BA t-butyl acrylate-   EA ethyl acrylate-   EHA ethylhexyl acrylate-   n-BA n-butyl acrylate-   HEMA hydroxyethyl methacrylate-   HEA hydroxyethyl acrylate-   HPA hydroxypropyl acrylate-   NtBAEMA N-tert-butylaminoethyl methacrylate-   VI vinylimidazole-   DMAPMA N-[3-(dimethylamino)propyl]methacrylamide-   w/w in the weight ratio-   AI active ingredient

DME dimethyl ether TABLE 1 Copolymers according to the invention withoutN-vinyllactams (component b)) NtBA DMA Ex. EMA t-BA VP VCap MAA AA EMAVI PMA Method 1 75 — — — 24 — — — 1 A 2 75 — — — 20 3 — — 2 A 3 70 — — —24 3 — — 3 A 4 73 — — — 25 — 2 — — A 5 72 — — — 22 3 3 — — A 6 72 — — —20 5 3 — — A 7 70 — — — 24 3 3 — — A 8 78 — — — 20 — —  2 — A 9 75 — — —23 2 —  5 — A 10 72 — — — 22 3 —  3 — A 11 65 — — — 25 5 —  5 — A 12 55— — — 25 10  — 10 — A 13 50 15 — — 25 5 —  5 — A

The dissolved copolymers according to the invention withoutN-vinyllactams of Tab.1 were 100% neutralized with AMP(2-amino-2-methylpropanol). TABLE 2 Copolymers according to theinvention comprising N-vinyllactams (component b)) NtBA DMA Ex. EMA t-BAVP VCap MAA AA EMA VI PMA Method 14 65 — 10 — 23 — —  2 — B 15 58 — 20 —18 — 4 — — B 16 58 — 20 — 18 — —  4 — B 17 58 — 20 — 18 — — — 4 B 18 3018 20 — 18 — — — 4 B 19 50 — 30 — 15 — —  5 — B 20 50 — 30 — 13 — —  7 —B 21 50 — — 25 20 — —  5 — B 22 40 — — 35 20 — 5 — — B 23 50 — 30 10 10— B

The pH of the polymerization solutions of the copolymers according tothe invention with N-vinyllactams of Tab.2 were adjusted to a pH in therange from 8.0 to 8.4 using AMP (2-amino-2-methyl-propanol).

Measuring the Setting (Flexural Rigidity):

The setting of polymeric film formers was measured, apart from bysubjective assessment, also objectively in physical terms as flexuralrigidity of thin hair tresses which have been treated with the polymersolution and dried again. Here, a force transducer determines the forcerequired for the bending, while the overall measurement takes placeunder standardized conditions in a climatically controlled room at 65%relative atmospheric humidity.

To measure the flexural rigidity, 3.0% strength by weight solutions ofthe polymers according to the invention are prepared. The flexuralrigidity measurement was carried out on 5 to 10 hair tresses (each about3 g and 24 cm in length) at 20° C. and 65% relative humidity. Theweighed, dry hair tresses were dipped into the 3.0% strength by weightpolymer solution, uniform distribution being ensured by immersion andremoval three times. The excess film former solution was then strippedoff between thumb and forefinger and the hair tresses were thencarefully squeezed by squeezing between filter paper. The tresses werethen shaped by hand to give a round cross section. Drying is carried outovernight in a climatically controlled room at 20° C. and 65% relativehumidity.

The experiments were carried out in a climatically controlled room at20° C. and 65% relative humidity by means of a tension/compressiontesting device. The hair tress was placed symmetrically on twocylindrical rolls of the sample holder. The tress was then bent exactlyin the middle from above using a rounded punch by 40 mm (breakage of thepolymer film). The force required for this was measured using a weighingcell (50 N) and given in Newtons.

1) Determination of the K value

The K values are measured in accordance with Fikentscher,Cellulosechemie, vol. 13, pp. 58 to 64 (1932) at 25° C. inaqueous/ethanolic or ethanolic solution and represent a measure of themolar weight. The aqueous/ethanolic or ethanolic solution of thepolymers comprises 1 g of polymer in 100 ml of solution. When thepolymers are in the form of aqueous dispersions, appropriate amounts ofthe dispersion depending on the polymer content of the dispersion aretopped up to 100 ml with ethanol so that the concentration of 1 g ofpolymer in 100 ml of solution arise.

The K value is measured in a Micro-Ubbelohde capillary type M Ic fromSchott. Flexural DMAP K rigidity Example EMA MMA VP MAA VI MAM value[cN] 23 50 — 30 10 10 — 39.5 380 cN

APPLICATION EXAMPLES Example A1

VOC 80 aerosol hair spray % by weight Polymer from Example No. 1 12.00(30% strength aqueous-ethanolic dispersion) Water 13.60 Dimethyl ether40.00 Ethanol 34.40 Further additive: silicone, perfume, antifoam . . .

The example can be repeated with the polymers of Examples 2-13. In eachcase, a VOC 80 aerosol hair spray with good properties is obtained.

Example A1a)

VOC-80 aerosol hair spray % by weight Polymer from Example No. 14 12.00(30% strength aqueous-ethanolic dispersion) Water 11.60 Dimethyl ether40.00 Ethanol 36.40 Further additive: silicone, perfume, antifoam . . .

The example can be repeated with the polymers of Examples 15-22. In eachcase, a VOC 80 aerosol hair spray with good properties is obtained.

Example A2

VOC 80 aerosol hair spray % by weight Polymer from Example No. 1 12.00(30% strength aqueous-ethanolic dispersion) Ultrahold ®Strong 1.0 Water12.20 Dimethyl ether 40.00 Ethanol 34.40 Aminomethylpropanol (95%strength) 0.40 Further additive: silicone, perfume, antifoam . . .

The example can be repeated with the polymers of Examples 2 to 13. Ineach case, a VOC 80 aerosol hair spray with good properties is obtained.

Example A3

VOC 80 aerosol hair spray % by weight Polymer from Example No. 1 12.00(30% strength aqueous-ethanolic dispersion) Luviset P.U.R. 5.0 (30%strength aqueous-ethanolic solution) Water 07.10 Dimethyl ether 40.00Ethanol 35.90 Aminomethylpropanol (95% strength) to pH 8.3 Furtheradditive: silicone, perfume, antifoam . . .

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a VOC 80 aerosol hair spray with good properties is obtained.

Example A4

VOC 55 aerosol hair spray % by weight Polymer from Example No. 1 15.00(30% strength aqueous-ethanolic dispersion) Water 37.00 Dimethyl ether40.00 Ethanol 8.00 Further additive: silicone, perfume, antifoam . . .

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a VOC 55 aerosol hair spray with good properties is obtained.

Example A5

VOC 55 aerosol hair spray % by weight Polymer from Example No. 1 12.00(30% strength aqueous-ethanolic dispersion) Luviset ®P.U.R. (30%aqueous-ethanolic dispersion) 3.00 Water 35.90 Dimethyl ether 40.00Ethanol 9.10 Further additive: silicone, perfume, antifoam . . .

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a VOC 55 aerosol hair spray with good properties is obtained.

Example A6

VOC 55 aerosol hair spray % by weight Polymer from Example No. 1 12.00(30% strength aqueous-ethanolic dispersion) Luvimer ® Pro55 (30%strength dispersion) 3.00 Water 35.90 Dimethyl ether 40.00 Ethanol 8.80Aminomethylpropanol (95% strength) 0.30 Further additive: silicone,perfume, antifoam . . .

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a VOC 55 aerosol hair spray with good properties is obtained.

Example A7

VOC 55 aerosol hair spray % by weight Polymer from Example No. 1 12.00(30% strength aqueous-ethanolic dispersion) Stepanhold ® R-1 ^(*)) (Fa.Stepan Chemical Co.) 1.00 Water 37.40 Dimethyl ether 40.00 Ethanol 9.40Aminomethylpropanol (95% strength) 0.20 Further additive: silicone,perfume, antifoam . . .^(*)) Stepanhold R-1 = poly(vinylpyrrolidone/ethylmethacrylate/methacrylic acid)

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a VOC 55 aerosol hair spray with good properties is obtained.

Example A8

VOC 55 pump spray % by weight Polymer from Example No. 1 15.00 (30%strength aqueous-ethanolic dispersion) Water 37.00 Ethanol 48.00 Furtheradditive: silicone, perfume, antifoam . . .

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a VOC 55 pump spray with good properties is obtained.

Example A9

VOC 55 pump spray % by weight Polymer from Example No. 1 12.00 (30%strength aqueous-ethanolic dispersion) Luviset ® Clear ^(*)) (BASF AG)20% strength 5.00 Water 33.60 Ethanol 49.40 Further additive: silicone,perfume, antifoam . . .^(*)) Luviset ® Clear =poly(vinylpyrrolidone/methacrylamide/vinylimidazole)

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a VOC 55 pump spray with good properties is obtained.

Example A10

VOC <10 pump spray % by weight Polymer from Example No. 1 12.00 (30%strength aqueous-ethanolic dispersion) Luviset ® Clear ^(*)) (BASF AG)20% strength 5.00 Water 83.00Further additive: silicone, perfume, antifoam . . .^(*)) Luviset ® Clear =poly(vinylpyrrolidone/methacrylamide/vinylimidazole)

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a VOC 55 pump spray with good properties is obtained.

Example A11

Setting foam % by weight Polymer from Example No. 1 10.00 (30% strengthaqueous-ethanolic dispersion) Luviset ® Clear ^(*)) (BASF AG) 20%strength 5.00 Cremophor ® A 25 (Ceteareth 25/BASE) 0.20 Comperlan ® KD(Coamide DEA/Henkel) 0.10 Water 74.20 Propane/butane 10.00 Furtheradditive: perfume, preservative . . .Preparation: Weigh in and dissolve with stirring. Bottle and addpropellant gas.

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a VOC 55 pump spray with good properties is obtained.

Example A12

Hair gel containing Aculyn ® 28: % by weight Phase 1: Polymer fromExample No. 1 12.00 (30% strength aqueous-ethanolic dispersion) Water,dist. 37.00 Aminomethylpropanol (38% strength solution) 1.0 Furtheradditive: preservative, soluble ethoxylated silicone, perfume . . .Phase 2: Aculyn ® 28 (1% strength aqueous suspension) 50.00

Preparation: Phases 1 and 2 are weighed in and homogenized separately.Phase 2 is then slowly stirred into phase 1. An almost clear, stable gelis formed.

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, a hair gel containing Aculyn 28 with good properties isobtained.

Example A13

Hair gel containing hydroxyethylcellulose % by weight Phase 1: Polymerfrom Example No. 1 12.00 (30% strength aqueous-ethanolic dispersion)Water, dist. 30.00 Further additive: preservative, soluble ethoxylatedsilicone, perfume . . . Phase 2: Natrosol ® HR 250 (5% strengthsolution) 50.00 Hydroxyethylcellulose (Hercules)Preparation:

Phases 1 and 2 are weighed in and homogenized separately. Phase 2 isthen slowly stirred into phase 1. An essentially clear, stable gel isformed.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a hair gel containing hydroxyethylcellulose with goodproperties is obtained.

Example A14

Conditioner shampoo % by weight A) Texapon ® NSO 28% strength 50.00(sodium laureth sulfate/Henkel) Comperlan ® KS (Coamide DEA/Henkel) 1.00Polymer from Example No. 14 12.00 (30% strength aqueous-ethanolicdispersion) q. s. perfume oil B) Water 27.5 Sodium chloride 1.5 q. s.preservative . . .Preparation:

Phases 1 and 2 are weighed in and homogenized separately. Phase 2 isthen slowly stirred into phase 1. An essentially, clear, stable gel isformed.

The example can be repeated with the polymers of Examples 15 to 22. Ineach case, a conditioner shampoo with good properties is obtained.

Example A15 Standard O/W Cream

Standard O/W Cream % by weight CTFA name Oil phase: Cremophor ® A6 3.5Ceteareth-6 (and) Stearyl Alcohol Cremophor ® A25 3.5 Ceteareth-25Glycerol monostearate 2.5 Glyceryl Stearate s.e. Paraffin oil 7.5Paraffin Oil Cetyl alcohol 2.5 Cetyl Alcohol Luvitol ®EHO 3.2 CetearylOctanoate Vitamin E acetate 1.0 Tocopheryl Acetate Nip-Nip 0.1Methyl-and Propyl 4-hydroxybenzoate (7:3) Water phase: Polymer from 3.0Example No. 14 (30% strength aqueous ethanol dispersion) Water 74.61,2-Propylene glycol 1.5 propylene glycol Germall ® II 0.1imidazolidinylureaPreparation:

The oil and water phases are weighed in separately and homogenized at atemperature of about 80° C. The water phase is then slowly stirred intothe oil phase and slowly cooled to room temperature with stirring.

The example can be repeated with the polymers of Examples 15 to 22. Ineach case, a standard O/W cream with good properties is obtained.

Example A16

Sunscreen gel % by weight Phase A 1.00 hydrogenated castor oil PEG-408.00 octylmethoxycinnamate (Uvinul ®MC 80 from BASF) 5.00 octocrylene(Uvinul ®N 539 from BASF) 0.80 octyltriazone (Uvinul ®T 150 from BASF)2.00 butylmethoxydibenzoylmethane (Uvinul BMBM from BASF) 2.00tocopheryl acetate q.s. perfume oil Phase B 10.00  polymer 1 (30%strength aqueous-ethanol. dispersion) 0.30 acrylate/C₁₀₋₃₀ alkylacrytate copolymer 0.20 carbomer 5.00 glycerol 0.20 disodium EDTA q.s.preservative 65.30  dist. water Phase C 0.20 sodium hydroxidePreparation:

Mix the components of phase A. Allow phase B to swell and stir intophase A with homogenization. Neutralize with phase C and homogenizeagain.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a sunscreen gel with good properties is obtained.

Example A17

Body lotion foam % by weight Phase A 1.50 ceteareth-25 1.50 ceteareth-64.00 cetearyl alcohol 10.00  cetearyl octanoate 1.00 dimethicone Phase B3.00 polymer 1 (30% strength aqueous-ethanol, dispersion) 2.00 panthenol2.50 propylene glycol q.s. preservative 74.50  dist. water Phase C q.s.perfume oilPreparation:

Heat phases A and B separately to about 80° C. Stir phase B into phase Aand homogenize. Cool to about 40° C., add phase C and briefly homogenizeagain. Bottling: 90% active ingredient and 10% propane/butane at 3.5 bar(20° C.).

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a body lotion foam with good properties is obtained.

Example A18

Shaving foam % by weight 6.00 ceteareth-25 5.00 poloxamer 407 52.00 dist. water 1.00 triethanolamine 5.00 propylene glycol 1.00 lanolin oilPEG-75 5.00 polymer 1 according to the invention (30% strengthaqueous-ethanol. dispersion) q.s. preservative q.s. perfume oil 25.00 sodium laureth sulfatePreparation:

Weigh everything together, then stir until dissolved. Bottling: 90 partsof active ingredient and 10 parts of propane/butane 25:75 mixture.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a shaving foam with good properties is obtained.

Preparation:

Dissolve phase A. Sprinkle phase B into phase A and dissolve. Add phaseC and leave to stir under reduced pressure at RT for about 45 min.

Example A19

Shower gel % by weight 50.00  sodium laureth sulfate, magnesium laurethsulfate, sodium laureth-8 sulfate, magnesium laureth-8 1.00 cocoamideDEA 4.00 polymer 1 (30% strength aqueous-ethanol. dispersion) 2.00sodium laureth sulfate, glycol distearate, cocamide MEA, laureth-10 q.s.preservative q.s. perfume oil 2.00 sodium chloride 41.00  dist. waterPreparation:

Weigh in all of the components together and stir until dissolved.

The example can be repeated with the polymers of Examples 2 to 7. Ineach case, a shower gel with good properties is obtained.

Example A20

Shower gel % by weight 30.00  sodium laureth sulfate 6.00 sodiumcocoamphodiacetate 6.00 cocamidopropylbetaine 3.00 sodium laurethsulfate, glycol distearate, cocamide MEA, laureth-10 7.70polyquaternium-44 1.50 polymer 1 (25% strength aqueous dispersion) 1.00panthenol q.s. preservative q.s. perfume oil q.s. citric acid 0.50sodium chloride 44.30  dist. waterPreparation:

Weigh in the components of phase A and dissolve. Adjust the pH to 6 to7.

The example can be repeated with the polymers of Examples 2 to 7. Ineach case, a shower gel with good properties is obtained.

Example A20a

Shower bath % by weight A 40.00  sodium laureth sulfate 5.00 sodiumC₁₂₋₁₅ pareth-15 sulfonate 5.00 decyl glucoside q.s. perfume oil 0.10phytantriol B 35.80  dist. water 0.1  guar hydroxypropyltrimoniumchloride 10.00  polymer 1 (30% strength-ethanol, dispersion) 1.00panthenol q.s. preservative 1.00 laureth-3 q.s. citric acid 2.00 sodiumchloridePreparation:

Mix the components of phase A. Add the components of phase B one afterthe other and mix. Adjust the pH to 6 to 7.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a shower bath with good properties is obtained.

Example A21

Liquid soap % by weight A 43.26  dist. water 0.34 aminomethylpropanol3.40 poly(ethyl acrylate/methacrylic acid) (Luviflex ®Soft, BASF) B40.00  sodium laureth sulfate 10.00  cocamidopropylbetaine 1.00 polymer1 (20% strength aqueous dispersion) q.s. perfume oil q.s. preservative2.00 sodium chloridePreparation:

Weigh in the components of phase A and dissolve until clear. Add thecomponents of phase B one after the other and mix.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a liquid soap with good properties is obtained.

Example A22

Freshening gel % by weight A 0.60 carbomer 45.40 dist. water B 0.50bisabolol 0.50 farnesol q.s. perfume oil 5.00 PEG-40 hydrogenated castoroil 2.50 polymer 1 (30% strength aqueous-ethanol. dispersion) 1.00tetrahydroxypropylethylenediamine 1.50 menthol 43.00  alcohol q.s. C. I.74 180, Direct Blue 86Preparation:

Allow phase A to swell. Dissolve phase B. Stir phase B into phase A.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a freshening gel with good properties is obtained.

Example A23

Aerosol hair foam % by weight A 2.00 cocotrimonium methsulfate 0.20perfume oil B 63.90  dist. water 6.70 polymer 1 (25% strength aqueousdispersion) 0.50 poly(ethyl acrylate/methacrylic acid) (Luviflex ®Soft,BASF) 0.10 aminomethylpropanol 0.20 ceteareth-25 0.20trimethylsilylamodimethicone, trideceth-10, cetrimonium chloride 0.10PEG-25 PABA 0.20 hydroxyethylcelluiose 0.20 PEG-8 0.20 panthenol 15.00 alcohol C 10.00  propane/butane 3.5 bar (2000)Preparation:

Mix phases A and B and bottle with propellant gas.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, an aerosol hair foam with good properties is obtained.

Example A24

Pump mousse % by weight A 2.00 cocotrimonium methosulfate q.s. perfumeoil C 74.30  dist. water 7.00 polyquaternium-46 (10% strength aqueoussolution) 15.00  polymer 1 (20% strength aqueous dispersion) 0.50 PEG-81.00 panthenol q.s. preservative 0.20 PEG-25 PABA (ethoxylatedp-aminobenzoic acid)

Preparation: Mix the components of phase A. Add the components of phaseB one after the other and dissolve to give a clear solution.

The example can be repeated with the polymers of Examples 2 to 7. Ineach case, a pump mousse with good properties is obtained.

Example A25

Aerosol foam % by weight 10.00  polymer 1 (30% strength aqueous-ethanol.dispersion) 5.00 PVP/VA copolymer (40% strength aqueous solution) 0.50hydroxyethylcetyldimonium phosphate 0.20 ceteareth-25 0.40 perfume oilPC 910.781/Cremophor 73.90  dist. water q.s. preservative 10.00 propane/butane 3.5 bar (20° C.)

Preparation: Weigh everything together, stir until dissolved, thenbottle.

The example can be repeated with the polymers of Examples 2 to 20. Ineach case, an aerosol foam with good properties is obtained.

Example A26 Color Styling Mousse

Color Styling Mousse % by weight A 2.00 cocotrimonium methosulfate q.s.perfume oil B 20.00  polymer 14 (30% strength aqueous-ethanol,dispersion) 0.50 acrylate copolymer (Luvimer ®100 P, BASF) 0.10aminomethylpropanol 0.20 ceteareth-25 0.20 panthenol 0.20hydroxyethylcellulose 10.00  alcohol 56.67  dist. water 0.08 C.I. 12245,Basic Red 76 0.05 C.I. 42510, Basic Violet 14 C 10.00  propane/butane3.5 bar (20° C.)

Preparation: Weigh everything together, stir until dissolved, thenbottle. Only suitable for dark blonde and brown hair!

The example can be repeated with the polymers of Examples 15 to 20. Ineach case, a color styling mousse with good properties is obtained.

Example A27

Pump hair foam % by weight A 1.50 cocotrimonium methosulfate q.s.perfume oil B 10.00  polymer 1 (20% strength aqueous dispersion) 86.04 dist. water C 0.46 aminomethylpropanol 4.00 PEG/PPG-25/25dimethicone/acrylate copolymer q.s. preservative

Preparation: Mix phase A. Stir phase B into phase A. Add phase C andstir until dissolved.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a pump hair foam with good properties is obtained.

Example A28

Aquawax % by weight 50.00  polymer 1 (20% strength aqueous dispersion)q.s. perfume oil q.s. hydrogenated castor oil PEG-40 0.10 diethylphthalate 0.10 cetearylethyl hexanoate 0.10 PEG-7 glyceryl cocoate 0.10preservative 47.70  dist. water 2.00 caprylic/capric triglyceride,acrylate copolymer

Preparation: Mix everything and homogenize. After-stir for 15 minutes.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, an aquawax with good properties is obtained.

Example A29

Shampoo % by weight 30.00  sodium laureth sulfate 6.00 sodiumcocoamphoacetate 6.00 cocamidopropylbetaine 3.00 sodium laureth sulfate,glycol distearate, cocamide MEA, laureth-10 3.00 polymer 1 (30% strengthaqueous-ethanol. dispersion) 2.00 dimethicone q.s. perfume q.s.preservative q.s. citric acid 1.00 sodium chloride ad 100 dist. waterPreparation:

Weigh in components and dissolve. Adjust pH to 6 to 7.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, a shampoo with good properties is obtained.

Example A30

Antidandruff shampoo % by weight 40.00  sodium laureth sulfate 10.00 cocamidopropylbetaine 10.00  disodium laureth sulfosuccinate 2.50 sodiumlaureth sulfate, glycol distearate, cocamide MEA, laureth-10 3.00polymer 1 ((30% strength aqueous-ethanol. dispersion) 0.50 climbazoleq.s. perfume q.s. preservative 0.50 sodium chloride ad 100 dist. waterPreparation:

Weigh in components and dissolve. Adjust pH to 6 to 7.

The example can be repeated with the polymers of Examples 2 to 22. Ineach case, an antidandruff shampoo with good properties is obtained.

Example A31

Clear shower gel % by weight 40.00  sodium laureth sulfate 5.00 decylglucoside 5.00 cocamidopropylbetaine 3.00 polymer 14 (30% strengthaqueous-ethanol. dispersion) 1.00 panthenol q.s. perfume q.s.preservative q.s. citric acid 2.00 sodium chloride ad 100 dist. waterPreparation:

Weigh in components and dissolve. Adjust pH to 6 to 7.

The example can be repeated with the polymers of Examples 15 to 22. Ineach case, a clear shower gel with good properties is obtained.

1-26. (canceled)
 27. A copolymer prepared by free-radical polymerizationof a monomer mixture M which comprises a) 30 to 80% by weight of ethylmethacrylate or  30 to 80% by weight of a mixture of ethyl methacrylateand at least one compound of the general formula I

wherein R¹ is H or CH₃, and R² is C₁-C₄-alkyl, with the proviso thatsaid at least one compound of general formula I is not ethylmethacrylate; b) 0 to 40% by weight of at least one N-vinyllactamcompound; c) 5 to 35% by weight of at least one monoethylenicallyunsaturated carboxylic acid; d) 0.1 to 30% by weight of at least onecompound containing a free-radically polymerizable, α,β-ethylenicallyunsaturated double bond and at least one cationogenic and/or cationicgroup per molecule; e) 0 to 20% by weight of additional free-radicallypolymerizable monomers, with the proviso that said additionalfree-radically polymerizable monomers are not the monomers of a), b),c), and d); wherein the fractions of components a), b), c), d), and e)add up to 100% by weight and wherein said monomer mixture M comprises atleast 20% by weight of ethyl methacrylate.
 28. The copolymer of claim27, wherein the ratio of the total molar amount of the carboxyl andcarboxylate groups to the total molar amount of the cationogenic andcationic groups is greater than or equal to
 2. 29. The copolymer ofclaim 27, wherein a) is ethyl methacrylate or a mixture comprising ethylmethacrylate and tert-butyl acrylate.
 30. The copolymer of claim 27,wherein b) is selected from the group consisting of N-vinylpyrrolidone,N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone,N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone,N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam,N-vinyl-7-ethyl-2-caprolactam, and mixtures thereof.
 31. The copolymerof claim 27, wherein c) consists of methacrylic acid or a mixture ofmethacrylic acid with at least one additional monoethylenicallyunsaturated carboxylic acid.
 32. The copolymer of claim 27, wherein c)consists of methacrylic acid or a mixture of methacrylic acid andacrylic acid.
 33. The copolymer of claim 31, wherein the weight ratio ofmethacrylic acid to said at least one additional monoethylenicallyunsaturated carboxylic acid in said mixture is greater than
 1. 34. Thecopolymer of claim 27, wherein d) comprises at least one compound with afree-radically polymerizable, α,β-ethylenically unsaturated double bondand at least one amino and/or ammonium group.
 35. The copolymer of claim34, wherein said at least one amino group is a primary, secondary, ortertiary amino group.
 36. The copolymer of claim 27, wherein d) isselected from the group consisting of esters of α,β-ethylenicallyunsaturated mono- and dicarboxylic acids with amino alcohols, whereinsaid amino alcohols are optionally mono- or dialkylated on the aminenitrogen; amides of α,β-ethylenically unsaturated mono- and dicarboxylicacids with diamines having at least one primary or secondary aminogroup; N,N-diallylamine; N,N-diallyl-N-alkylamines and derivativesthereof; vinyl- and allyl-substituted nitrogen heterocycles; vinyl- andallyl-substituted heteroaromatic compounds; and mixtures thereof. 37.The copolymer of claim 27, wherein monomer mixture M comprises a) in anamount of from 30 to 70% by weight; b) in an amount of from 10 to 40% byweight; c) in an amount of from 10 to 25% by weight; and d) in an amountof from 0.5 to 5% by weight.
 38. The copolymer of claim 27, whereinmonomer mixture M comprises a) in an amount of from 50 to 80% by weight;b) in an amount of from 0% by weight; c) in an amount of from 15 to 35%by weight; and d) in an amount of from 0.5 to 12% by weight.
 39. Thecopolymer of claim 27, wherein a) is ethyl methacrylate; b) isN-vinylpyrrolidone, N-vinylcaprolactam, or mixtures thereof; c) ismethacrylic acid or a mixture of methacrylic acid and acrylic acid; andd) is a monomer selected from the group consisting ofN-[3-(dimethylamino)propyl](meth)acrylamide, N-(tert-butyl)aminoethylmethacrylate, vinylimidazole, and mixtures thereof.
 40. A cosmetic orpharmaceutical composition comprising A) at least one copolymeraccording to claim 27; and B) at least one cosmetically orpharmaceutically acceptable carrier.
 41. The composition according toclaim 40, wherein the B) is water; water-miscible organic solvents;oils; fats; waxes; esters of C₆-C₃₀-monocarboxylic acids with mono-, di-or trihydric alcohols which are different from iii); saturated acyclicand cyclic hydrocarbons; fatty acids; fatty alcohols; propellant gases;or mixtures thereof.
 42. The composition of claim 40, additionallycomprising at least one additive different from A) and B) and which isselected from the group consisting of cosmetically active ingredients,emulsifiers, surfactants, preservatives, perfume oils, thickeners, hairpolymers, hair and skin conditioners, graft polymers, water-soluble ordispersible silicone-containing polymers, photoprotective agents,bleaches, gel formers, care agents, colorants, tinting agents, tanningagents, dyes, pigments, bodying agents, humectants, regreasing agents,collagen, protein hydrolyzates, lipids, antioxidants, antifoams,antistats, emollients, and softeners.
 43. The composition of claim 40,additionally comprising at least one nonionic, anionic or ampholyticpolymer.
 44. The composition of claim 43, wherein said anionic polymeris a polyurethane.
 45. The composition of claim 40, wherein the acidgroups present in said composition are at least partially neutralized bysilicone polymers comprising amino groups.
 46. The composition of claim40, wherein said composition is in the form of a gel, foam, spray,mousse, ointment, cream, emulsion, suspension, lotion, milk or paste.47. The composition of claim 40, wherein said composition has a fractionof volatile organic components equal to or less than 80% by weight. 48.A skin-cleansing composition, a compositions for the care and protectionof the skin, a nail care composition, a preparation for decorativecosmetics, or a hair-treatment composition comprising a copolymeraccording to claim
 27. 49. A hair-treatment composition setting agent orconditioner comprising a copolymer according to claim
 27. 50. Ahair-treatment composition according to claim 48, wherein saidcomposition is in the form of a hair gel, shampoo, setting foam, hairtonic, hairspray, or hair foam.
 51. A pharmaceutical auxiliary; arheological modifier; a surface-active compound; an adhesive; or atextile, paper, printing, or leather coating comprising the copolymeraccording to claim
 27. 52. A method for preparing copolymers accordingto claim 27 comprising the steps of a) free-radically polymerizing themonomer mixture M comprising the components a), b), c), d) and ifappropriate e) at a pH in the range of from 5 to 8; b) whenpolymerization is complete, adjusting the pH to a value in the range offrom 5 to 7; c) steam distilling the polymerization solution, d) aftersteam distillation, optionally adjusting the pH of the distilledpolymerization solution to a value in the range of from 7.5 to 9.0.